Composition for forming anti-reflective coating for use in lithography

ABSTRACT

There is provided a composition for forming anti-reflective coating for anti-reflective coating that has a good absorption of light at a wavelength utilized for manufacturing a semiconductor device, that exerts a high protection effect against light reflection, that has a high dry etching rate compared with the photoresist layer. Concretely, the composition for forming anti-reflective coating contains a triazine trione compound, oligomer compound or polymer compound having hydroxyalkyl structure as substituent on nitrogen atom.

This application is a continuation of application Ser. No. 10/530,349filed Apr. 6, 2005 which is a National Stage of PCT Application No.PCT/JP03/12875, filed Oct. 8, 2003 that claims priority to JP2002-295777 filed Oct. 9, 2002 and 2003-126886, filed May 2, 2003. Theentire disclosures of the prior applications are hereby incorporated byreference.

TECHNICAL FIELD

The present invention relates to a composition for forminganti-reflective coating, particularly to a composition for reducing areflection of irradiation light for exposing a photoresist applied on asubstrate from the substrate in a lithography process for manufacturinga semiconductor device, and more particularly to a composition forforming anti-reflective coating comprising a compound, an oligomercompound or a polymer compound that effectively absorbs reflection lightfrom the substrate in a lithography process for manufacturing asemiconductor device by use of irradiation light for exposure with awavelength of 248 nm, 193 nm or 157 nm.

BACKGROUND ART

Conventionally, in the manufacture of semiconductor devices,micro-processing by lithography using a photoresist composition has beencarried out. The micro-processing is a processing method includingforming a thin film of a photoresist composition on a semiconductorsubstrate such as a silicon wafer, irradiating actinic rays such asultraviolet rays through a mask pattern on which a pattern for asemiconductor device is depicted, developing it to obtain a photoresistpattern, and etching the semiconductor substrate using the photoresistpattern as a protective film. However, in recent progress in highintegration of semiconductor devices, there has been a tendency thatshorter wavelength actinic rays are being used, i.e., ArF excimer laserbeam (wavelength 193 nm) have been taking the place of i-line(wavelength 365 nm) or KrF excimer laser beam (wavelength 248 nm). Alongwith this change, influences of random reflection and standing wave offa substrate have become serious problems. Accordingly, it has beenwidely studied to provide an anti-reflective coating between thephotoresist and the substrate (Bottom Anti-Reflective Coating, BARC).

As the anti-reflective coating, inorganic anti-reflective coatings madeof titanium, titanium dioxide, titanium nitride, chromium oxide, carbonor α-silicon and organic anti-reflective coatings made of alight-absorbing substance and a polymer compound are known. The formerrequires an installation such as a vacuum deposition apparatus, a CVD(chemical vapor deposition) apparatus or a sputtering apparatus. Incontrast, the latter is considered advantageous in that it requires nospecial installation so that many studies have been made. For example,mention may be made of the acrylic resin type anti-reflective coatinghaving a hydroxyl group being a crosslinking reaction group and a lightabsorbing group in the same molecule and the novolak resin typeanti-reflective coating having a hydroxyl group being a crosslinkingreaction group and a light absorbing group in the same molecule (see,for example U.S. Pat. Nos. 5,919,599 and 5,693,691).

The physical properties desired for organic anti-reflective coatingmaterials include high absorbance to light and radioactive rays, nointermixing with the photoresist layer (being insoluble in photoresistsolvents), no diffusion of low molecular substances from theanti-reflective coating material into the topcoat resist upon coating orheat-drying, and a higher dry etching rate than the photoresist (see,for example, Tom Lynch et al., “Properties and Performance of Near UVReflectivity Control Layers”, US, in Advances in Resist Technology andProcessing XI, Omkaram Nalamasu ed., Proceedings of SPIE, 1994, Vol.2195, p. 225-229; G. Taylor et al., “Methacrylate Resist andAntireflective Coatings for 193 nm Lithography”, US, in Microlithography1999: in Advances in Resist Technology and Processing XVI, Will Conleyed., Proceedings of SPIE, 1999, Vol. 3678, p.174-185; and Jim D. Meadoret al., “Recent Progress in 193 nm Antireflective Coatings, US, inMicrolithography 1999: in Advances in Resist Technology and ProcessingXVI, Will Conley ed., Proceedings of SPIE, 1999, Vol. 3678, p. 800-809).

In recent years, miniaturization of process dimension in lithographyprocess by use of KrF excimer laser beam or ArF excimer laser beam, thatis, miniaturization of photoresist pattern to be formed is progressing.With the progress in the miniaturization of photoresist pattern, it isdesired to make photoresist thinner in order to avoid collapse ofphotoresist pattern. When the photoresist is used in a form of thinfilm, it is desired that an organic anti-reflective coating usedtogether with it can be removed for a short time in order to depressreduction in film thickness of the photoresist layer in a step ofremoving the organic anti-reflective coating by etching. That is, forreduction in time for etching removing step, it is required that anyorganic anti-reflective coating can be used in a form of thinner film,or that the organic anti-reflective coating has a larger selection ratioof etching rate with photoresist than the prior one.

By the way, a hitherto technique of anti-reflective coatings has beenmainly considered on lithography process with irradiation light having awavelength of 365 nm, 248 nm or 193 nm. As a result of suchconsideration, light absorbing components and light absorbing groupseffectively absorbing light of each wavelength are developed, and theycome to be utilized as one component of an organic anti-reflectivecoating composition. For example, it is known that chalcone diesprepared by condensation of 4-hydroxyacetophenone with4-methoxybenzaldehyde are effective for irradiation light having awavelength of 365 nm (see, for example Japanese Patent Laid-open No. Hei11-511194), it is known that naphthalene group-containing polymershaving a specific structure have high absorbance for irradiation lighthaving a wavelength of 248 nm (see, for example Japanese PatentLaid-open No. Hei 10-186671), and it is known that resin bindercompositions containing phenyl unit are excellent for irradiation lighthaving a wavelength of 193 nm (see, for example Japanese PatentLaid-open No. 2000-187331).

In addition, it is known that tris(hydroxyalkyl)isocyanurate substitutedwith aromatic compound or alicyclic compound is used as a broad UVabsorber (see, for example Japanese Patent Laid-open No. Hei 11-279523),and that a curing composition contains cyanuric acid as a polymerizableorganic compound (see, for example Japanese Patent Laid-open No. Hei10-204110). An anti-reflective coating composition containing cyanuricacid derivative is also known (see, for example WO 02/086624). Further,it is disclosed that a polyester synthesized from1,3,5-tris(2-hydroxyethyl)cyanuric acid is used for an anti-reflectivecoating (see, for example EP 1298492 A and EP 1298493 A).

In recent years, lithography process with F2 excimer laser (wavelength157 nm) being a light source having a shorter wavelength comes to beregarded as next-generation technology in place of that with ArF excimerlaser (wavelength 193 nm). It is considered that the former processpermits micro-processing of process dimension not more than 100 nm, andat present its development and research have been actively carried outfrom the aspects of apparatus and material, etc. However, most of theresearch on material relate to photoresist, and it is an actualcondition that the research on organic anti-reflective coatings islittle known. This is because components effectively absorbing lighthaving a wavelength of 157 nm, that is light absorbing components havinga strong absorption band at 157 nm are little known.

It is considered that as irradiation light provides process dimensionnot more than 100 nm. Therefore, it is also considered that aphotoresist is used in a form of thin film having a thickness of 100 to300 nm that is thinner compared with the prior one. Organicanti-reflective coatings used along with such a photoresist in a form ofthin film require the followings: they can be used in a form of a thinfilm; and they have a high selectivity of dry etching for photoresist.And, it is considered that organic anti-reflective coatings are requiredto have a large attenuation coefficient k so that they could be used ina shape of thin film having a thickness of 30 to 80 nm. In a simulationwith PROLITH ver. 5 (manufactured by Litho Tech Japan; expected andideal values are used as optical constants (refractive index,attenuation coefficient) of the photoresist), an anti-reflective coatinghaving a base substrate made of silicon with a thickness of 30 to 80 nmcan have second minimum thickness (about 70 nm), and in this case thecoating has an attenuation coefficient k of 0.3 to 0.6 and a reflectancefrom substrate of 2% or less, thus has a sufficient anti-reflectiveeffect. In addition, a similar simulation in which silicon oxide is usedas base substance and a thickness of silicon oxide varies between 100 nmand 200 nm results in that attenuation coefficient k of 0.4 to 0.6 isrequired in order to exert a sufficient anti-reflective effect with ananti-reflective coating having a thickness of 70 nm. For example, incase where attenuation coefficient k is 0.2, reflectance from substratevaries between 5% and 10%, and in case where attenuation coefficient kis 0.4, reflectance from substrate varies between 0% and 5%.Consequently, it is considered that in order to exert a sufficientanti-reflective effect, a high attenuation coefficient k, for example0.3 or more is required. However, any material for organicanti-reflective coatings satisfying such an attenuation coefficient khave been little known.

Under such circumstances, it is demanded to develop organicanti-reflective coatings efficiently absorbing reflection light from asubstrate and thereby having an excellent anti-reflective effect.Further, photoresists for lithography process for which irradiationlight from F2 excimer laser are used are actively examined at present,and therefore it is considered that many kinds of photoresists will bedeveloped in future. And, it is considered that a method of changingattenuation coefficient so as to suit required characteristics of eachphotoresist, for example a method of changing attenuation coefficient kcomes to be important.

The present invention relates to a composition for forminganti-reflective coating, which has a strong absorption of light at ashort wavelength, particularly light at wavelength of 248 nm, 193 nm or157 nm. In addition, the present invention provides a composition forforming anti-reflective coating, which can be used in a lithographyprocess for manufacturing a semiconductor device carried out by usingirradiation light from KrF excimer laser (wavelength 248 nm), ArFexcimer laser beam (wavelength 193 nm) or F2 excimer laser (wavelength157 nm). Further, the present invention provides an anti-reflectivecoating for lithography which effectively absorbs reflection light froma substrate when irradiation light from KrF excimer laser, ArF excimerlaser beam or F2 excimer laser is used for micro-processing, and whichcauses no intermixing with photoresist layer, can be rapidly removed inthe following removal step, and has a high dry etching rate comparedwith the photoresists. In addition, the present invention provides amethod of forming an anti-reflective coating for lithography by usingthe composition for forming anti-reflective coating, and a method offorming a photoresist pattern.

DISCLOSURE OF INVENTION

The present invention relates to the following aspects:

-   -   as a first aspect, a composition for forming anti-reflective        coating characterized in that the composition comprises a        triazine trione compound having hydroxyalkyl structure as        substituent on nitrogen atom, a triazine trione oligomer        compound having hydroxyalkyl structure as substituent on        nitrogen atom, or a triazine trione polymer compound having        hydroxyalkyl structure as substituent on nitrogen atom;    -   as a second aspect, the composition for forming anti-reflective        coating as described in the first aspect, wherein the triazine        trione compound having hydroxyalkyl structure as substituent on        nitrogen atom is a compound of formula (1):

wherein A₁, A₂ and A₃ are independently of one another hydrogen atom,methyl or ethyl, X is —OC(═O)—, —S—, —O— or —NR— wherein R is hydrogenatom or methyl, M is benzene ring, naphthalene ring or anthracene ringwhich may be substituted with C₁₋₆ alkyl, phenyl, naphthyl, halogenatom, C₁₋₆ alkoxycarbonyl, nitro, cyano, C₁₋₆ alkoxy or C₁₋₆ alkylthio;

-   -   as a third aspect, the composition for forming anti-reflective        coating as described in the first aspect, wherein the triazine        trione compound having hydroxyalkyl structure as substituent on        nitrogen atom, the triazine trione oligomer compound having        hydroxyalkyl structure as substituent on nitrogen atom, or the        triazine trione polymer compound having hydroxyalkyl structure        as substituent on nitrogen atom is a triazine trione compound        having a substituent of formula (2) or (3) as substituent on        nitrogen atom, or a triazine trione oligomer compound or        triazine trione polymer compound having a structure in which at        least two triazine trione rings are linked through a linking        group of formula (4) or (5) on the nitrogen atoms:

wherein A₁, A₂ and A₃ have the same meaning above, each Y isindependently a direct bond or —C(═O)—, Ar is benzene ring ornaphthalene ring which may be substituted with C₁₋₆ alkyl, phenyl,naphthyl, halogen atom, C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆alkoxy, hydroxy, thiol, C₁₋₆ alkylthio or amino, Q is C₁₋₆ alkyl, C₅₋₈cycloalkyl, Ar or —CH₂—Ar—CH₂—, R₁ is C₁₋₆ alkyl, phenyl or benzyl, R₂is hydrogen atom, C₁₋₆ alkyl, phenyl or benzyl;

-   -   as a fourth aspect, the composition for forming anti-reflective        coating as described in the third aspect, wherein the triazine        trione compound having a substituent of formula (2) or (3) has a        structure of formula (6) or (7):

wherein A₁, A₂, A₃, Y, Ar, R₁ and R₂ have the same meaning above;

-   -   as a fifth aspect, the composition for forming anti-reflective        coating as described in the third aspect, wherein the triazine        trione oligomer compound or triazine trione polymer compound        having a structure in which at least two triazine trione rings        are linked through a linking group of formula (4) or (5) on the        nitrogen atoms has a structure of formula (8) or (9):

wherein A₁, A₂, A₃, Y, Ar, Q, R₁ and R₂ have the same meaning mentionedabove;

-   -   as a sixth aspect, the composition for forming anti-reflective        coating as described in the first aspect, wherein the triazine        trione oligomer compound having hydroxyalkyl structure as        substituent on nitrogen atom, or triazine trione polymer        compound having hydroxyalkyl structure as substituent on        nitrogen atom is a reaction product of a compound of        formula (10) with a compound of formula (11) or (12):

wherein R₃ is C₁₋₆ alkyl, C₃₋₆ alkenyl, phenyl, benzyl or2,3-epoxypropyl, R₄ and R₅ are C₁₋₆ alkyl, C₃₋₆ alkenyl, phenyl orbenzyl, R₆ is C₁₋₆ alkyl, phenyl, benzyl or —(CH₂)_(n)COOH, and n is anumber of 1, 2 or 3;

-   -   as a seventh aspect, the composition for forming anti-reflective        coating as described in the third aspect, wherein the triazine        trione compound having a substituent of formula (2) as        substituent on nitrogen atom, or the triazine trione oligomer        compound or triazine trione polymer compound having a structure        in which at least two triazine trione rings are linked through a        linking group of formula (4) on the nitrogen atoms is produced        from a triazine trione compound having at least two nitrogen        atoms having a substituent of formula (13) on nitrogen atom and        a phenyl compound or naphthalene compound of formula (14) having        at least two substituents selected from carboxy and hydroxy        which are identical or different from each other

wherein A₁, A₂, A₃, Y and Ar have the same meaning above;

-   -   as an eighth aspect, the composition for forming anti-reflective        coating as described in seventh aspect, wherein triazine trione        compound having at least two nitrogen atoms having a substituent        of formula (13) on nitrogen atom is a triazine trione compound        of formula (15)

wherein A₁, A₂ and A₃ have the same meaning above;

-   -   as a ninth aspect, the composition for forming anti-reflective        coating as described in the seventh aspect, wherein the phenyl        compound or naphthalene compound of formula (14) is at least one        compound selected from the group consisting of compounds of        formulae (16) to (21)

wherein B is hydrogen atom, C₁₋₆ alkyl, phenyl, naphthyl, halogen atom,C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆ alkoxy, hydroxy, thiol,C₁₋₆ alkylthio or amino, n is a number of 1 to 6, m is a number of 1 to4, and B may be identical with or different from each other in casewhere n or m is 2 or more;

-   -   as a tenth aspect, the composition for forming anti-reflective        coating as described in any one of the first to ninth aspects,        further containing a crosslinking agent having at least two        crosslink-forming substituents;    -   as an eleventh aspect, the composition for forming        anti-reflective coating as described in any one of the first to        tenth aspects, further containing an acid and/or an acid        generator;    -   as a twelfth aspect, the composition for forming anti-reflective        coating as described in any one of the first to eleventh        aspects, further containing a resin having at least one        crosslinking-forming substituent selected from hydroxy, carboxy,        amino and thiol;    -   as a thirteenth aspect, an anti-reflective coating produced by        coating the composition for forming anti-reflective coating as        described in any one of the first to twelfth aspects on a        semiconductor substrate, and baking it, wherein the        anti-reflective coating has an attenuation coefficient k to a        light at a wavelength of 248 nm ranging from 0.40 to 0.65;    -   as a fourteenth aspect, an anti-reflective coating produced by        coating the composition for forming anti-reflective coating as        described in any one of the first to twelfth aspects on a        semiconductor substrate, and baking it, wherein the        anti-reflective coating has an attenuation coefficient k to a        light at a wavelength of 157 nm ranging from 0.20 to 0.50;    -   as a fifteenth aspect, an anti-reflective coating produced by        coating the composition for forming anti-reflective coating as        described in any one of the first to twelfth aspects on a        semiconductor substrate, and baking it, wherein the        anti-reflective coating has an attenuation coefficient k to a        light at a wavelength of 193 nm ranging from 0.20 to 0.60;    -   as a sixteenth aspect, a method of forming an anti-reflective        coating for use in a manufacture of a semiconductor device,        comprising the steps of: coating the composition for forming        anti-reflective coating as described in any one of the first to        twelfth aspects on a substrate, and baking it;    -   as a seventeenth aspect, a method of forming an anti-reflective        coating for use in a manufacture of a semiconductor device by        use of a light of wavelength 248 nm, 193 nm or 157 nm,        comprising the steps of: coating the composition for forming        anti-reflective coating as described in any one of the first to        twelfth aspects on a substrate, and baking it;    -   as an eighteenth aspect, a method of forming a photoresist        pattern for use in a manufacture of a semiconductor device        comprising the steps of:    -   coating the composition for forming anti-reflective coating as        described in any one of the first to twelfth aspects on a        semiconductor substrate and baking it to form an anti-reflective        coating,    -   forming a photoresist layer on the anti-reflective coating,    -   exposing the semiconductor substrate covered with the        anti-reflective coating and the photoresist layer with a light,        and    -   developing the exposed photoresist layer; and    -   as a nineteenth aspect, the method of forming a photoresist        pattern as described in the eighteenth aspect, wherein the        exposure is carried out with a light of wavelength 248 nm, 193        nm or 157 nm.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a composition for forminganti-reflective coating characterized in that the composition comprisesa triazine trione compound having hydroxyalkyl structure as substituenton nitrogen atom, a triazine trione oligomer compound havinghydroxyalkyl structure as substituent on nitrogen atom, or a triazinetrione polymer compound having hydroxyalkyl structure as substituent onnitrogen atom. In addition, the present invention relates to acomposition for forming anti-reflective coating, which can be used inlithography process for manufacturing a semiconductor device by use ofirradiation light of a short wavelength, particularly irradiation lightof KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength193 nm) or F2 excimer laser (wavelength 157 nm).

The composition for forming anti-reflective coating according to thepresent invention basically comprises a triazine trione compound havinghydroxyalkyl structure as substituent on nitrogen atom, a triazinetrione oligomer compound having hydroxyalkyl structure as substituent onnitrogen atom, or a triazine trione polymer compound having hydroxyalkylstructure as substituent on nitrogen atom, and a solvent; and asarbitrary component a catalyst for crosslinking, a surfactant and thelike. The composition for forming anti-reflective coating according tothe present invention contains 0.1 to 50 mass %, for example 0.5 to 30mass % of solid content. In this specification, the solid content meanscomponents other than the solvent in the composition for forminganti-reflective coating.

The triazine trione compound having hydroxyalkyl structure assubstituent on nitrogen atom, triazine trione oligomer compound havinghydroxyalkyl structure as substituent on nitrogen atom, or triazinetrione polymer compound having hydroxyalkyl structure as substituent onnitrogen atom in the composition for forming anti-reflective coatingaccording to the present invention is contained in an amount of 10 mass% or more, for example 30 mass % to 99 mass %, for example 50 mass % to99 mass %, and further 60 mass % to 95 mass % per 100 mass % of thetotal solid content.

In the composition for forming anti-reflective coating according to thepresent invention, as the triazine trione compound having hydroxyalkylstructure as substituent on nitrogen atom, the compound of formula (1)may be mentioned. In formula (1), A₁, A₂ and A₃ are independently of oneanother hydrogen atom, methyl or ethyl, X is —OC(═O)—, —S—, —O— or —NR—wherein R is hydrogen atom or methyl, M is benzene ring, naphthalenering or anthracene ring which may be substituted with C₁₋₆ alkyl,phenyl, naphthyl, halogen atom, C₁₋₆ alkoxycarbonyl, nitro, cyano, C₁₋₆alkoxy or C₁₋₆ alkylthio.

The compound of formula (1) can be obtained, for example by the reactionof a compound of formula (15) with a compound of formula (22):

wherein X is —OC(═O)—, —S—, —O— or —NR— wherein R is hydrogen atom ormethyl, M is benzene ring, naphthalene ring or anthracene ring which maybe substituted with C₁₋₆ alkyl, phenyl, naphthyl, halogen atom, C₁₋₆alkoxycarbonyl, nitro, cyano, C₁₋₆ alkoxy or C₁₋₆ alkylthio.

The reaction of the compound of formula (15) with the compound offormula (22) is preferably carried out in a solution state in which theyare dissolved in an organic solvent such as benzene, toluene, xylene,ethyl lactate, butyl lactate, propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, N-methyl pyrrolidone or thelike. In the reaction, the compound of formula (15) with the compound offormula (22) can be used in only one compound, respectively, or in acombination of two or more. In addition, in the reaction, quaternaryammonium salt such as benzyl triethyl ammonium chloride, tetrabutylammonium chloride, tetraethyl ammonium bromide or the like can be usedas a catalyst for the reaction. The reaction temperature and reactiontime depend on the compounds to be used or the concentration thereof orthe like, but the reaction time is suitably selected from 0.1 to 100hours, and the reaction temperature is suitably selected from 20° C. to200° C. When the catalyst is used, it may be used in an amount of 0.001to 50 mass % based on the total mass of used compounds.

In the composition for forming anti-reflective coating containing thecompound of formula (1) according to the present invention, thecharacteristics of the anti-reflective coating formed from thecomposition for forming anti-reflective coating, particularly lightabsorption characteristics, attenuation coefficient, refractive indexand the like to irradiation light used for lithography process largelydepend on the kind of the compound of formula (22) used. The kind of thecompound of formula (22) used affects the time required for the removalstep of the anti-reflective coating formed from the composition forforming anti-reflective coating according to the present invention byetching. In particular, the kind and number of substituents on benzenering, naphthalene ring or anthracene ring on the compound of formula(22) affect the time required for the removal step of anti-reflectivecoating by etching. The introduction of substituent containing heteroatom such as halogen atom, nitrogen atom, oxygen atom, sulfur atom orthe like, or the increase in the number thereof can make possible toreduce time required for the removal step by etching.

In case where the composition for forming anti-reflective coatingcontaining the compound of formula (1) according to the presentinvention is applied for a process with a light of wavelength 248 nm(KrF excimer laser), the compound of formula (22) having naphthalenering or anthracene ring (M is naphthalene ring or anthracene ring) ispreferably used. In addition, in case where it is applied for a processwith a light of wavelength 193 nm (ArF excimer laser) or wavelength 157nm (F2 excimer laser), the compound having benzene ring (M is benzenering) is preferably used.

The compound of formula (15) used for obtaining the compound of formula(1) includes for example tris-(2,3-epoxypropyl)-isocyanurate,tris-(2-methyl-2,3-epoxypropyl)-isocyanurate,tris-(2,3-epoxybutyl)-isocyanurate, or the like.

The compound of formula (22) used for obtaining the compound of formula(1) includes for example benzoic acid, monoethyl isophthalate,2,4-dibromobenzoic acid. 4-methylbenzoic acid, 2-methoxybenzoic acid,2,3,5-triiodo benzoic acid, 2-chloro-4-nitorbenzoic acid,4-fluorobenzoic acid, 4-iodobenzoic acid, 4-bromobenzoic acid,4-t-butylbenzoic acid, 3-trifluoromethylbenzoic acid, 2-nitrobenzoicacid, 4-isopropoxybenzoic acid, 3-cyanobenzoic acid, 3-phenylbenzoicacid, 3-bromo-4-methylbenzoic acid, 2,4,6-tribromobenzoic acid,4-methylthiobenzoic acid, 2-bromo-4-fluorobenzoic acid or the like.

In addition, the compound of formula (22) includes for examplenaphthalene-2-carboxylic acid, 1-bromonaphthalene-2-carboxylic acid,4-bromo-3-methoxy-naphthalene-2-carboxylic acid,3-methylnaphthalene-2-carboxylic acid, 4-fluoro naphthalene-1-carboxylicacid, 4-nitoronaphthalene-1-carboxylic acid, 5-bromonaphthalene-1-carboxylic acid, 8-iodonaphthalene-1-carboxylic acid,anthracene-9-carboxylic acid, anthracene-2-carboxylic acid,10-bromoanthracene-9-carboxylic acid or the like.

Further, the compound of formula (22) includes for example phenol,4-methylphenol, 4-chlorophenol, 4-bromophenol, 4-nitrophenol,2,3,4,5-tetrabromophenol, pentabromophenol, 4-bromo-2-fluorophenol,4-iodophenol, 2,4,6-triiodophenol, 2,5-dimethyl-4-iodophenol,4-methylthiophenol, 3-methoxyphenol, 3-bromophenol, 2-cyanophenol,2,6-diiodo-4-cyanophenol, 3-hydroxy methyl benzoate, 2-naphthol,1-bromo-2-naphthol, 2-nitro-1-naphthol, 2-methyl-1-naphthol,4-methoxy-1-naphthol, 2,4-dichloro-1-naphthol,2-hydroxynaphthalnene-3-carboxylic acid methyl ester,2-hydroxyanthracene, 9-hydroxyanthracene or the like.

In addition, the compound of formula (22) includes for example aniline,3-chloroaniline, 2-bromoaniline, 4-iodoaniline, 3-methoxyaniline,3-methylthioaniline, 4-nitroaniline, 3-isopropylaniline,3,5-dibromoaniline, 2-fluoro-4-iodoaniline, 2-amino-5-iodobenzoic acidmethyl ester, 2,4,6-tribromoaniline, 4-bromo-3-methylaniline,2-bromo-4-nitroaniline, 2-bromo-5-trifluoromethylaniline,3-phenylaniline, 1-aminonaphthalene, 1-amino-4-bromonaphthalene,1-amino-2-nitronaphthalene, 1-aminoanthracene, 9-aminoanthracene or thelike.

Further, the compound of formula (22) includes for example thiophenol,2-methylthiophenol, 4-chlorothiophenol, pentachlorothiophenol,3-methoxythiophenol, 3-bromothiophenol, 2-mercaptobenzoic acid methylester, 4-nitrothiophenol, 3-iodothiophenol, 1-naphthalenethiol,9-mercaptoanthracene or the like.

In addition, as compounds to be reacted with the compound of formula (8)include, in addition to the compounds of formula (15), for examplecompounds having carboxy or hydroxy, such as thiophen-2-carboxylic acid,5-bromothiophen-2-carboxylic acid, phenylacetic acid, 4-bromophenoxyacetic acid, benzyl alcohol, 2,4-dibromobenzylalcohol, 3-bromo cinnamicacid, 9-hydroxymethylanthracene, thiazole-2-carboxylic acid,2-amino-5-bromothiazole can be used.

As the compound of formula (1) contained in the composition for forminganti-reflective coating according to the present invention, for examplethe compound of formula (23) (Compound No. 1 in Table 1 below) and thecompound of formula (24) (Compound No. 15 in Table 1 below) may bementioned:

Similarly, the compounds shown in Table 1 may be mentioned (in Table, Phmeans phenyl, 1-Nap means 1-naphthyl, 2-Nap means 2-naphthyl, and 9-Antmeans 9-anthryl).

TABLE 1 Compound No. A1 A2 A3 X M 1 H H H OC(═O) Ph-2,4-(Br)₂ 2 H H HOC(═O) Ph 3 H H H OC(═O) Ph-4-NO₂ 4 H CH₃ H OC(═O) Ph 5 H H H OC(═O)Ph-3-CN 6 H H H OC(═O) Ph-3-CH₃ 7 H H H OC(═O) Ph-2-OCH₃ 8 H H H OC(═O)Ph-2,3,5-(I)₃ 9 H CH₃ H OC(═O) Ph-3-Br-5-I 10 H H H OC(═O)Ph-2,3,4,5-(I)₄ 11 H H H OC(═O) Ph-3-SCH₃ 12 H H H OC(═O) Ph-2,4-(Cl)₃13 H H H OC(═O) Ph-2-Br-4-CH₃ 14 H H H OC(═O) Ph-3-Br-5-I 15 H H HOC(═O) 1-Nap-6-OCH₃ 16 H H H OC(═O) 2-Nap-3-CH₃ 17 H CH₃ H OC(═O) 1-Nap18 H H H OC(═O) 2-Nap-6-F 19 H H H OC(═O) 9-Ant 20 H H H OC(═O)9-Ant-10-Br 21 H H H S Ph-4-F 22 H H H S Ph 23 H H H S Ph-3-CH₃ 24 H H HS Ph-2,4-(Cl)₃ 25 H H H S Ph-2,4-(Br)₂ 26 H H H S 1-Nap 27 H H H S2-Nap-6,7-(Br)₂ 28 H H H S 9-Ant 29 H H H NH Ph 30 H CH₃ H NH Ph 31 H HH NH Ph-4-CH₃ 32 H H H NH Ph-2-Br 33 H H H NH Ph-3,5-(Br)₂ 34 H H H NHPh-3-CN 35 H H H NH Ph-3-COOCH₃ 36 H H H NH Ph-3,4,5-(Cl)₃ 37 H H H NHPh-4-SCH₃ 38 H H H NH Ph-2-F-4-Cl 39 H H H NH Ph-3-CH₃ 40 H H H NH 1-Nap41 H H H O Ph-2-Br 42 H CH₃ H O Ph 43 H H H O Ph-2,4-Br₂ 44 H H H OPh-4-CH₃ 45 H H H O Ph-3-I 46 H H H O Ph-2-F 47 H H H O Ph-3-OCH₃ 48 H HH O Ph-3-NO₂ 49 H H H O 1-Nap-2-Cl 50 H CH₃ H O 1-Nap 51 H H H O 2-Nap52 H H H O 9-Ant

In the composition for forming anti-reflective coating according to thepresent invention, the compound of formula (1) may be used alone or in amixture of two or more. The content of the compound of formula (1) is 10mass % or more, for example 30 mass % to 99 mass %, for example 50 mass% to 99 mass %, further for example 60 to 95 mass % in the total solidcontent.

In the composition for forming anti-reflective coating according to thepresent invention, as the triazine trione compound having hydroxyalkylstructure as substituent on nitrogen atom, a triazine trione compoundhaving a substituent of formula (2) or (3) as substituent on nitrogenatom, or a triazine trione oligomer compound or triazine trione polymercompound having a structure in which at least two triazine trione ringsare linked through a linking group of formula (4) or (5) on the nitrogenatoms may be mentioned. In formula (2), (3), (4) or (5), A₁, A₂ and A₃are independently of one another hydrogen atom, methyl or ethyl, Y is adirect bond or —C(═O)—, Ar is benzene ring or naphthalene ring which maybe substituted with C₁₋₆ alkyl, phenyl, naphthyl, halogen atom,C₁₋₆alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆ alkoxy, hydroxy, thiol,C₁₋₆ alkylthio or amino, Q is C₁₋₆ alkyl, C₅₋₈ cycloalkyl, Ar or—CH₂—Ar—CH₂—, R₁ is C₁₋₆alkyl, phenyl or benzyl, R₂ is hydrogen atom,C₁₋₆ alkyl phenyl or benzyl.

As the triazine trione compound having a substituent of formula (2), thecompounds having a structure of formula (6) can be used. In formula (6),A₁, A₂ and A₃ are independently of one another hydrogen atom, methyl orethyl, Y is a direct bond or —C(═O)—, Ar is benzene ring or naphthalenering which may be substituted with C₁₋₆ alkyl, phenyl, naphthyl, halogenatom, C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆ alkoxy, hydroxy,thiol, C₁₋₆alkylthio or amino.

The compound of formula (6) can be obtained by reacting a triazinetrione compound having on nitrogen atom a substituent of formula (13):

wherein A₁, A₂ and A₃ are independently of one another hydrogen atom,methyl or ethyl, with a phenyl compound or a naphthalene compound offormula (14):

HO—Y—Ar—Y—OH   (14)

wherein Y is a direct bond or —C(═O)—, Ar is benzene ring or naphthalenering which may be substituted with C₁₋₆ alkyl, phenyl, naphthyl, halogenatom, C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆ alkoxy, hydroxy,thiol, C₁₋₆ alkylthio or amino. In this reaction, the compound offormula (14) can be used alone or in a combination of two or more. Thereaction is preferably carried out in a solution state in which they aredissolved in an organic solvent such as benzene, toluene, xylene, ethyllactate, butyl lactate, propylene glycol monomethyl ether, propyleneglycol monomethyl ether acetate, N-methyl pyrrolidone or the like. Inaddition, quaternary ammonium salt such as benzyl triethyl ammoniumchloride, tetrabutyl ammonium chloride, tetraethyl ammonium bromide orthe like can be used as a catalyst for the reaction. The reactiontemperature and reaction time depend on the compounds to be used or theconcentration thereof or the like, but the reaction time is suitablyselected from 0.1 to 100 hours, and the reaction temperature is suitablyselected from 20° C. to 200° C. When the catalyst is used, it may beused in an amount of 0.001 to 50 mass % based on the total mass of usedcompounds.

In the triazine trione compound having the substituent of formula (13),compounds having one, two or three nitrogen atoms having the substituentof formula (13) on nitrogen atom are assumed, all of them can be used inthis reaction or they can be used in a combination of them. Thecompounds having three substituents of formula (13), that is, thecompound of formula (15) is preferably used. The compounds of formula(15) wherein A₁, A₂ and A₃ are hydrogen atom, methyl or ethyl, whereinA₁, A₂ and A₃ are hydrogen, and wherein A₁ and A₃ are hydrogen atom andA₂ is methyl are preferably used.

When the triazine trione compound having two or three nitrogen atomshaving the substituent of formula (13) is used, it is assumed that allsubstituents of them are reacted with the compound of formula (14) oronly one or two substituents are reacted with the compound of formula(14). The present invention include both cases. In the composition forforming anti-reflective coating according to the present invention, thecompounds obtained by reacting all substituents in the compound (15)having three substituents of formula (13) with the compound of formula(14) are preferably used, and the compound of formula (25) is preferablyused. In formula (25), Y is a direct bond or —C(═O)—, Ar is benzene ringor naphthalene ring which may be substituted with C₁₋₆ alkyl, phenyl,naphthyl, halogen atom, C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆alkoxy, hydroxy, thiol, C₁₋₆ alkylthio or amino.

The compounds of formula (14) to be reacted with the triazine trionecompound having the substituent of formula (13) on nitrogen atom includethe compounds of formulae (16) to (21):

wherein B is hydrogen atom, C₁₋₆ alkyl, phenyl, naphthyl, halogen atom,C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆-alkoxy, hydroxy, thiol,C₁₋₆alkylthio or amino, n is a number of 1 to 6, m is a number of 1 to4, and B may be identical with or different from each other in casewhere n or m is 2 or more. In this reaction, the compounds of formulae(16) to (21) can be used in only one or in a combination of two or more.

As the triazine trione compound having the substituent of formula (3) onnitrogen atom, the compounds having the structure of formula (7) can beused. In formula (7), A₁, A₂ and A₃ are independently of one anotherhydrogen atom, methyl or ethyl, R₁ is C₁₋₆ alkyl, phenyl or benzyl, R₂is hydrogen atom or C₁₋₆ alkyl. C₁₋₆ alkyl includes for example methyl,ethyl, n-pentyl, i-propyl, cyclohexyl or the like.

The compound of formula (7) can be produced by reacting the triazinetrione compound having the substituent of formula (13) on nitrogen atomwith carbon dioxide to convert epoxy ring moiety into dioxolanone ring,and then reacting with an amine compound of formula (26).

The reaction for converting epoxy ring moiety into dioxolanone ring canbe carried out by reacting with carbon dioxide for example in thepresence of lithium bromide. And, the reaction of dioxolanone ring withthe amine compound of formula (26) can be carried out for example inN,N-dimethylformamide at 70° C. for 48 hours.

When the triazine trione compound having two or three nitrogen atomshaving the substituent of formula (13) is used in this reaction, it isassumed that all epoxy ring moieties of them are converted intodioxolanone rings and then converted into the substituents of formula(3) or only one or two epoxy ring moieties are converted into thesubstituents of formula (3). The present invention include both cases.

As the triazine trione compound having the substituent of formula (13)on nitrogen atom, the compound having three substituents of formula(13), the compound of formula (15) is preferably used. In thecomposition for forming anti-reflective coating according to the presentinvention, the compound produced by converting all epoxy ring moietiesof the compound of formula (15) into the substituents of formula (3) ispreferably used, and the compound of formula (27) is preferably used.

wherein R₁ and R₂ have the same meaning above.

The compounds of formula (26) to be reacted with the triazine trionecompound having the substituent of formula (13) on nitrogen atom includefor example methylamine, ethylamine, isopropylamine, n-butylamine,cyclohexylamine, aniline, benzylamine, dimethylamine, diethylamine,diisopropylamine, dibenzylamine or diphenylamine. In this reaction, thecompound of formula (26) can be used in only one or in a combination oftwo or more.

In the composition for forming anti-reflective coating according to thepresent invention, the compound of formula (27) may be used alone or ina combination of two or more. The content of the compound of formula(27) is 10 mass % or more, for example 30 mass % to 99 mass %, forexample 50 mass % to 99 mass %, further for example 60 to 95 mass % inthe total solid content.

In the composition for forming anti-reflective coating containing thecompound of formula (27) according to the present invention, thecharacteristics of the anti-reflective coating formed from thecomposition for forming anti-reflective coating, particularly lightabsorption characteristics, attenuation coefficient, refractive indexand the like to irradiation light used for lithography process depend onthe kind of the compound of formula (26) used in the reaction.

In the composition for forming anti-reflective coating according to thepresent invention, as the triazine trione oligomer compound or triazinetrione polymer compound having a structure in which at least twotriazine trione rings are linked through a linking group of formula (4)on the nitrogen atoms, the triazine trione oligomer compound or triazinetrione polymer compound having the structure of formula (8) can be used.In formula (8), A₁, A₂ and A₃ are independently of one another hydrogenatom, methyl or ethyl, Y is a direct bond or —C(═O)—, Ar is benzene ringor naphthalene ring which may be substituted with C₁₋₆ alkyl, phenyl,naphthyl, halogen atom, C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆alkoxy, hydroxy, thiol, C₁₋₆ alkylthio or amino.

The weight average molecular weight of the triazine trione oligomercompound or triazine trione polymer compound having the structure offormula (8) in the composition for forming anti-reflective coatingaccording to the present invention is not specifically limited and isfor example 700 to 200000, and for example 1000 to 50000.

The triazine trione oligomer compound or triazine trione polymercompound having the structure of formula (8) can be obtained by reactingthe compounds having two or three nitrogen atoms having the substituentof formula (13) on nitrogen atom with the aromatic compound of formula(14). In this reaction, the compound of formula (14) can be used in onlyalone or in a combination of two or more.

This reaction is preferably carried out in a solution state in whichthey are dissolved in an organic solvent such as benzene, toluene,xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, N-methyl pyrrolidone or thelike. In addition, in the reaction, quaternary ammonium salt such asbenzyl triethyl ammonium chloride, tetrabutyl ammonium chloride,tetraethyl ammonium bromide or the like can be used as a catalyst forthe reaction. The reaction temperature and reaction time depend on thecompounds to be used or the concentration thereof or the like, but thereaction time is suitably selected from 0.1 to 100 hours, and thereaction temperature is suitably selected from 20° C. to 200° C. Whenthe catalyst is used, it may be used in an amount of 0.001 to 50 mass %based on the total mass of used compounds.

In this reaction, the triazine trione compound having two or threesubstituents of formula (13) on nitrogen atom can be used alone or in acombination of two or more. The compounds having three substituents offormula (13), that is, the compound of formula (15) is preferably used.

In this reaction, it is assumed that all substituents of the triazinetrione compound having two or three nitrogen atoms having thesubstituent of formula (13) are reacted with the compound of formula(14) to form liking groups of formula (4) or only one or twosubstituents of formula (13) are involved in the formation of thelinking group of formula (4) and the remaining substituent of formula(13) is unreacted or involved in the formation of the substituent offormula (2). In the triazine trione oligomer compound or the triazinetrione polymer compound, it is assumed that one or two substituents offormula (13) in the triazine compound being a raw material are involvedin the formation of the linking group of formula (4), that is, theformation of oligomer structure, polymer structure, and the remainingsubstituent of formula (13) is unreacted or involved in the formation ofthe substituent of formula (2), or that all (that is, two or three)substituents of formula (13) are involved in the formation of thelinking group of formula (4), that is, the formation of oligomerstructure, polymer structure.

In the production of the triazine trione oligomer compound or triazinetrione polymer compound according to this reaction, the compound offormula (15) being the compound having three substituents of formula(13) is preferably used, particularly the compound of formula (28) ispreferably used.

wherein A₄ is hydrogen atom or methyl.

The compound of formula (14) used for the preparation of the triazinetrione oligomer compound or triazine trione polymer compound having thestructure of formula (8) includes compounds having naphthalene ring orbenzene ring of formulae (16) to (21). These compounds can be used aloneor in a combination of two or more.

The composition for forming anti-reflective coating according to thepresent invention contains the triazine trione compound, triazine trioneoligomer compound or triazine trione polymer compound obtained by thereaction between the triazine trione compound having the substituent offormula (13) on nitrogen atom and the phenyl compound or naphthylcompound of formula (14). The composition for forming anti-reflectivecoating according to the present invention contains any compositionscontaining such a triazine trione compound, triazine trione oligomercompound or triazine trione polymer compound only, or containing amixture of the triazine trione compound and the triazine trione oligomercompound, a mixture of the triazine trione compound and the triazinetrione polymer compound, a mixture of the triazine trione oligomercompound and the triazine trione polymer compound, or a mixture of thetriazine trione compound, the triazine trione oligomer compound and thetriazine trione polymer compound.

In the composition for forming anti-reflective coating containing thetriazine trione compound, triazine trione oligomer compound or triazinetrione polymer compound produced by reaction between the triazine trionecompound having the substituent of formula (13) on nitrogen atom and thecompound of formula (14), according to the present invention, thecharacteristics of the anti-reflective coating formed from thecomposition for forming anti-reflective coating, particularly lightabsorption characteristics, attenuation coefficient, refractive indexand the like to irradiation light used for lithography process largelydepend on the kind of the compound of formula (14) used in the reaction.In addition, the kind of the compound of formula (14) used affects thetime required for the removal step of the anti-reflective coating formedfrom the composition for forming anti-reflective coating according tothe present invention by etching. In particular, the kind and number ofsubstituents on benzene ring or naphthalene ring on the compound offormula (14) affect the time required for the removal step ofanti-reflective coating by etching. The introduction of substituentcontaining halogen atom, nitrogen atom, oxygen atom, sulfur atom or thelike, or the increase in the number thereof can make possible to reducetime required for the removal step by etching.

In case where the composition for forming anti-reflective coatingaccording to the present invention is applied for a process with a lightof wavelength 248 nm (KrF excimer laser), the compound of formula (14)having naphthalene ring of formulae (16) to (18) is preferably used. Inaddition, in case where it is applied for a process with a light ofwavelength 193 nm (ArF excimer laser) or wavelength 157 nm (F2 excimerlaser), the compound having benzene ring of formulae (19) to (21) ispreferably used.

Such naphthalene ring-containing compounds include for example3-hydroxynaphthalene-2-carboxylic acid, naphthalene-2,6-dicarboxylicacid, naphthalene-2,3-dicarboxylic acid,1,6-dibromo-2-hydroxynaphthalene-3-carboxylic acid,6-hydroxynaphthalene-2-carboxylic acid,3,7-dihydroxynaphthalene-2-carboxylic acid,4-hydroxy-1-phenyl-naphthalene-2-carboxylic acid,6-hydroxynaphthalene-2-carboxylic acid,4-bromonaphthalene-1,8-dicarboxylic acid,2-hydroxynaphthalene-1-carboxylic acid,4-bromonaphthalene-1,4-dicarboxylic acid, 1,5-dihydroxynaphthalene,2,6-dibromo-1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,6-ethoxy-2,3-dihydroxynaphthalene or the like.

Such benzene ring-containing compounds include for example3-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid,2-amino-3-hydroxybenzoic acid, 2,5-dichloro-3-hydroxy-6-methoxybenzoicacid, 2,4,6-triiodo-3-hydroxybenzoic acid,2,4,6-tribromo-3-hydroxybenzoic acid,2-bromo-4,6-dimethyl-3-hydroxybenzoic acid, 2-fluoro-5-hydroxybenzoicacid, 3-methoxy4-hydroxybenzoic acid, 3,5-dibromo-4-hydroxybenzoic acid,2,4-dihydroxy-5-bromobenzoic acid, 3-iodo-5-nitro-4-hydroxybenzoic acid,2-hydroxybenzoic acid,4-chloro-2-hydroxybenzoic acid,3,5-diiodo-2-hydroxybenzoic acid, 3-methoxy-2-hydroxybenzoic acid,2-hydroxy-6-isopropyl-3-methylbenzoic acid,4-amino-3,5-diiodo-2-hydroxybenzoic acid,4,5-dichloro-benzene-1,3-dicarboxylic acid,5-amino-2,4,6-triiodoisophthalic acid, benzene-1,4-dicarboxylic acid,2,3,5,6-tetrabromo-benzene-1,4-dicarboxylic acid, 4,5-dichlorophthalicacid, 5-methoxy-3-methylphthalic acid, 3,4,5,6-tetrabromophathalic acidor the like.

In the composition for forming anti-reflective coating according to thepresent invention, as the triazine trione oligomer compound or triazinetrione polymer compound having a structure in which at least twotriazine trione rings are linked through a linking group of formula (5)on the nitrogen atoms, the triazine trione oligomer compound or triazinetrione polymer compound having the structure of formula (9) can be used.In formula (9), A₁, A₂ and A₃ are independently of one another hydrogenatom, methyl or ethyl, Q is C₁₋₆ alkyl or C₅₋₈ cycloalkyl, Ar or—CH₂—Ar—CH₂—, R₁ is C₁₋₆ alkyl, phenyl or benzyl, R₂ is hydrogen atom,C₁₋₆ alkyl, phenyl or benzyl.

The weight average molecular weight of the triazine trione oligomercompound or triazine trione polymer compound of formula (9) in thecomposition for forming anti-reflective coating according to the presentinvention is not specifically limited and is for example 700 to 200000,and for example 1000 to 50000.

The triazine trione oligomer compound or triazine trione polymercompound having the structure of formula (9) can be obtained by reactingthe triazine trione compound having the substituent of formula (13) onnitrogen atom with carbon dioxide to convert epoxy ring moiety intodioxolanone ring, and then reacting with an amine compound of formula(29).

The reaction of dioxolanone ring with the amine compound of formula (29)can be carried out for example in the presence of N,N-dimethylformamidesolvent at 70° C. for 48 hours. In this reaction, the compound offormula (29) can be used alone or in a combination of two or more.

In this reaction, the triazine trione compound having two or threenitrogen atoms having the substituent of formula (13) can be used aloneor in a combination of two or more. The compound having threesubstituents of formula (13), that is, the compound of formula (15) ispreferably used.

In this reaction, it is assumed that all epoxy ring moieties of thetriazine trione compound having two or three nitrogen atoms having thesubstituent of formula (13) are converted into dioxolanone ring, andthen reacted with the compound of formula (29) to form liking groups offormula (5) or only one or two epoxy ring moieties of formula (13) areinvolved in the formation of the linking group of formula (5) and theremaining substituent of formula (13) is unreacted or involved in theformation of the substituent of formula (3) wherein R₂ is hydrogen atom.In the triazine trione oligomer compound or the triazine trione polymercompound, it is assumed that one or two substituents of formula (13) inthe triazine compound being a raw material are involved in the formationof the linking group of formula (5), that is, the formation of oligomerstructure, polymer structure, and the remaining substituent of formula(13) is unreacted or involved in the formation of the substituent offormula (3), or that all (that is, two or three) substituents of formula(13) are involved in the formation of the linking group of formula (5),that is, the formation of oligomer structure, polymer structure.

In the production of the triazine trione oligomer compound or triazinetrione polymer compound according to this reaction, the compound offormula (15) being the compound having three substituents of formula(13) is preferably used, particularly the compound of formula (28) ispreferably used.

The compounds of formula (29) used for producing the triazine trioneoligomer compound or triazine trione polymer compound having thestructure of formula (9) include for example ethylenediamine,propylenediamine, phenylenediamine, 2-hydroxy-1,3-propylenediamine,1,4-cyclohexyldiamine, xylenediamine, 2,6-dichlorophenylenediamine,1,4-diaminonaphthalene, 1,5-diaminonaphthalene or the like. Thesecompounds can be used alone or in a combination of two or more.

In the composition for forming anti-reflective coating containing thetriazine trione compound, triazine trione oligomer compound or triazinetrione polymer compound having the structure of formula (9) according tothe present invention, the characteristics of the anti-reflectivecoating formed from the composition for forming anti-reflective coating,particularly light absorption characteristics, attenuation coefficient,refractive index and the like to irradiation light used for lithographyprocess largely depend on the kind of the compound of formula (29) usedin the reaction. In addition, the kind of the compound of formula (29)used affects the time required for the removal step of theanti-reflective coating formed from the composition for forminganti-reflective coating according to the present invention by etching.

In case where the composition for forming anti-reflective coatingaccording to the present invention is applied for a process with a lightof wavelength 248 nm (KrF excimer laser), compounds preferably used asthe compound of formula (29) are compounds having a naphthalene ring,such as 1,4-diaminonaphthalene, 1,5-diaminonaphthalene,2,3-diaminonaphthalene or the like. In addition, in case where it isapplied for a process with a light of wavelength 193 nm (ArF excimerlaser) or wavelength 157 nm (F2 excimer laser), compound having benzenering, such as phenylenediamine, xylenediamine,2,6-dichlorophenylenediamine, 3,5-dibromo-1,2-phenylenediamine,3,4,5,6-tetraiodo-1,2-phenylenediamine or the like are preferably used.

The substituent of formula (2) or (3) and the linking group of formula(4) or (5) in the triazine trione compound having the substituent offormula (2) or (3) as substituent on nitrogen atom, or the triazinetrione oligomer compound or triazine trione polymer compound having astructure in which at least two triazine trione rings are linked througha linking group of formula (4) or (5) on the nitrogen atoms, containedin the composition for forming anti-reflective coating according to thepresent invention include the followings.

For example, the substituent of formula (2) includes the substituents offormulae (30) to (37):

For example, the substituent of formula (3) includes the substituents offormulae (38) to (43):

Further, the linking group of formula (4) includes for example thesubstituents of formulae (44) to (52):

In addition, the linking group of formula (5) includes for example thesubstituents of formulae (54) to (55):

In the composition for forming anti-reflective coating according to thepresent invention, the triazine trione compound having hydroxyalkylstructure as substituent on nitrogen atom includes also a reactionproduct of a compound of formula (10) with a compound of formula (11) or(12). R₃ is C₁₋₆ alkyl, C₃₋₆ alkenyl, phenyl, benzyl or 2,3-epoxypropyl,R₄ and R₅ are C₁₋₆ alkyl, C₃₋₆ alkenyl, phenyl or benzyl, R₆ is C₁₋₆alkyl, phenyl, benzyl or —(CH₂)_(n)COOH, n is a number of 1, 2 or 3.C₁₋₆ alkyl is for example methyl, ethyl, n-pentyl, isopropyl, cyclohexylor the like. C₃₋₆ alkenyl is for example allyl, 2-butenyl, 3-butenyl,2-pentenyl or the like.

The compound of formula (10) and the compound of formula (11) providethe compound consisting of the structural unit of formula (56) as areaction product by reacting them in a solvent such as cyclohexanone orpropylene glycol monomethyl ether, etc. by use of benzyltriethylammonium bromide as a catalyst under reflux with heating.

In case where R₃ is 2,3-epoxypropyl in formula (10), all of three epoxyring moieties can be reacted with the compound of formula (11), and canprovide the compound having the structural unit of formula (57).

The number of the structural unit of formulae (56) and (57) contained inthe reaction product varies depending on the reaction condition. Thereaction product used in the composition for forming anti-reflectivecoating according to the present invention contains the structural unitof formula (56) of 1 to 10000, and oligomer compounds or polymercompounds of weight average molecular weight of 400 to 1000000 arepreferably used. In addition, oligomer compounds or polymer compoundscontaining the structural unit of formula (57) of 1 to 10000 and havinga weight average molecular weight of 400 to 1000000 are preferably used.

The compound of formula (10) and the compound of formula (12) provide areaction product by reacting them in a solvent such as cyclohexanone orpropylene glycol monomethyl ether, etc. by use of benzyltriethylammonium bromide as a catalyst under reflux with heating. In case whereR₆ is C₁₋₆ alkyl, phenyl or benzyl in formula (12), a reaction productis provided by the reaction between one carboxy of formula (12) and theepoxy ring of formula (10). In case where R₆ is —(CH₂)_(n)COOH informula (12), the reaction product consisting of the structural unit offormula (58) is provided by the reaction between two carboxy groupsthereof and respective epoxy ring of formula (10).

In case where R₃ is 2,3-epoxypropyl in formula (10), all of three epoxyring moieties can be reacted with the carboxy groups of formula (12),and can provide the compound having the structural unit of formula (59).

The number of the structural unit of formulae (58) and (59) contained inthe reaction product varies depending on the reaction condition. Thereaction product used in the composition for forming anti-reflectivecoating according to the present invention contains the structural unitof formula (58) of 1 to 10000, and oligomer compounds or polymercompounds of weight average molecular weight of 400 to 1000000 arepreferably used. In addition, oligomer compounds or polymer compoundscontaining the structural unit of formula (59) of 1 to 10000 and havinga weight average molecular weight of 400 to 1000000 are preferably used.

In the composition for forming anti-reflective coating according to thepresent invention, the reaction product containing the structural unitof formulae (56) can be used in a combination with the reaction productcontaining the structural unit of formulae (58).

The compound of formula (10) used for the production of the reactionproduct includes for example monoallyldiglycidyl isocyanuric acid,monomethyldiglycidyl isocyanuric acid, monoethyidiglycidyl isocyanuricacid, monobutyidiglycidyl isocyanuric acid, monophenyldiglycidylisocyanuric acid, monobenzyldiglycidyl isocyanuric acid.

The compound of formula (11) includes for example monoallyl isocyanuricacid, monomethyl isocyanuric acid, monoethyl isocyanuric acid, monobutylisocyanuric acid, monophenyl isocyanuric acid, monobenzyl isocyanuricacid.

And, the compound of formula (12) includes for example dimethylmonocarboxyethyl isocyanuric acid, diethyl monocarboxyethyl isocyanuricacid, diallylcarboxyethyl isocyanuric acid, dibutyl monocarboxyethylisocyanuric acid, diphenyl monocarboxyethyl isocyanuric acid, dibenzylmonocarboxyethyl isocyanuric acid.

The anti-reflective coating forming composition according to the presentinvention is preferably crosslinked after application by heating inorder to prevent intermixing with a photoresist applied thereon. Inaddition, the anti-reflective coating forming composition according tothe present invention may further contain a crosslinking agentcomponent. The crosslinking agent includes melamines and substitutedureas having crosslink-forming substituents such as methylol ormethoxymethyl groups, or polymer compounds having epoxy groups, and thelike. Preferable crosslinking agents are ones having at least twocrosslink-forming substituents, for example, compounds such asmethoxymethylated glycoluril, methoxymethylated melamine, morepreferably tetramethoxymethyl glycoluril or hexamethoxymethyl melamine.Further, the crosslinking agents include compounds such astetramethoxymethyl urea or tetrabutoxymethyl urea. The addition amountof the crosslinking agent may vary depending on the coating solventsused, the underlying substrate used, the viscosity of the solutionrequired, the shape of the coating required, etc., and usually 0.001 to20 mass %, preferably 0.01 to 15 mass %, more preferably 0.05 to 10 mass% in the total composition. These crosslinking agents occasionally occura crosslinking reaction due to self-condensation, but they can becross-reacted with a crosslink-forming substituent on the triazinetrione compound having hydroxyalkyl structure as substituent on nitrogenatom, triazine trione oligomer compound having hydroxyalkyl structure assubstituent on nitrogen atom, or triazine trione polymer compound havinghydroxyalkyl structure as substituent on nitrogen atom contained inanti-reflective coating forming composition according to the presentinvention, for example hydroxy in formula (1), (2), (3), (4), (5), (56),(57), (58) or (59).

As catalyst for promoting the above-mentioned crosslinking reaction inthe present invention, acid compounds, such as p-toluenesulfonic acid,trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylicacid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoicacid, etc. and/or thermal acid generators, such as2,4,4,6-tetrabromocyclohexadienone, benzointosylate,2-nitrobenzyltosylate, etc. may be added. The blending amount thereof is0.02 to 10 mass %, for example 0.04 to 5 mass % in the total solidcontent.

The composition for forming anti-reflective coating according to thepresent invention can further contain a resin having at lease onecrosslink-forming substituent selected from hydroxy group, carboxygroup, amino group and thiol group. The addition of such a resin enablesthe adjustment of characteristics such as refractive index, attenuationcoefficient, etching rate or the like of the anti-reflective coatingformed from the composition for forming anti-reflective coatingaccording to the present invention. The resin can include one containingas a structural unit 2-hydroxyethylacrylate, 2-hydroxypropylacrylate,2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, vinyl alcohol,2-hydroxyethyl vinyl ether, acrylic acid, methacrylic acid or the like.The resin has a weight average molecular weight of preferably 500 to1,000,000, more preferably 500 to 500,000 or 1,000 to 100,000. Theamount of the resin in the composition for forming anti-reflectivecoating is 20 mass % or less, preferably 15 mass % or less in the totalsolid content.

The resin includes for example poly 2-hydroxyethyl methacrylate,polyvinyl alcohol, polyacrylic acid, a copolymer of 2-hydroxypropylacrylate with methyl methacrylate, a copolymer of 2-hydroxypropylacrylate with isopropyl methacrylate, a copolymer of 2-hydroxypropylmethacrylate with 2,2,2-trichloroethyl methacrylate, a copolymer of2-hydroxypropyl methacrylate with 2,2,2-trifluoroethyl methacrylate, acopolymer of 2-hydroxypropyl methacrylate with 2-chloroethylmethacrylate, a copolymer of 2-hydroxypropyl methacrylate withcyclohexyl methacrylate, a copolymer of 2-hydroxypropyl methacrylatewith n-octyl methacrylate, a copolymer of 2-hydroxypropyl methacrylatewith vinyl alcohol, a copolymer of 2-hydroxypropyl methacrylate withacrylic acid, a copolymer of 2-hydroxypropyl methacrylate withmaleimide, a copolymer of 2-hydroxypropyl methacrylate withacrylonitrile, a copolymer of vinyl alcohol with methyl methacrylate, acopolymer of vinyl alcohol with maleimide, a copolymer of vinyl alcoholwith methyl methacrylate, a copolymer of 2-hydroxyethyl vinyl ether withethyl methacrylate, a copolymer of 2-hydroxyethyl vinyl ether with2-hydroxypropyl methacrylate, a copolymer of methacrylic acid with ethylmethacrylate, a copolymer of methacrylic acid with maleimide, or thelike.

The anti-reflective coating composition according to the presentinvention may contain photoacid generators in order to adjust theacidity to that of a photoresist applied thereon in the lithographyprocess. Preferable photoacid generators include for example onium saltphotoacid generators, such as bis(4-t-butylpheny)iodoniumtrifluoromethanesulfonate or triphenylsulfoniumtrifluoromethanesulfonate, halogen-containing photoacid generators, suchas phenyl-bis(trichloromethyl)-s-triazine, sulfonate photoacidgenerators, such as benzoin tosylate or N-hydroxysuccinimidetrifluoromethanesulfonate. The photoacid generators are added in anamount of 0.2 to 3 mass %, preferably 0.4 to 2 mass % in the total solidcontent.

Light absorbing compounds or light absorbing resins can be added to thecomposition for forming anti-reflective coating according to the presentinvention. The addition of the light absorbing compounds or lightabsorbing resins enables the adjustment of characteristics such asrefractive index, attenuation coefficient, etching rate or the like ofthe anti-reflective coating formed from the composition for forminganti-reflective coating according to the present invention. These lightabsorbing compounds or light absorbing resins include ones having a highabsorptivity to a light in photosensitive characteristics wavelengthregion of the photosensitive component in the photoresist layer formedon the anti-reflective coating and preventing standing wave due toreflection from the substrate or random reflection due to unevenness onthe surface of substrate. Further, the light absorbing resin used has aweight average molecular weight of 500 to 1,000,000, preferably 500 to500,000, or 1,000 to 10,000.

The light absorbing compound or light absorbing resin can be used aloneor in a mixture of two or more. The amount of the light absorbingcompound or light absorbing resin in the composition for forminganti-reflective coating according to the present invention is preferably0.01 mass % or more, 1 to 90 mass %, for example 1 to 50 mass %, or forexample 5 to 40 mass % in the total solid content.

As the light absorbing compound, for example the following compounds arepreferably used: phenyl compounds, benzophenone compounds, benzotriazolecompounds, azo compounds, naphthalene compounds, anthracene compounds,anthraquinone compounds, triazine compounds, triazine trione compounds,quinoline compounds or the like. Phenyl compounds, naphthalenecompounds, anthracene compounds, triazine compounds and triazine trionecompounds are preferably used.

Phenyl compounds having at least one hydroxy group, amino group orcarboxy group, naphthalene compounds having at least one hydroxy group,amino group or carboxy group, and anthracene compounds having at leastone hydroxy group, amino group or carboxy group are preferably used.

The phenyl compounds having at least one hydroxy group, amino group orcarboxy group include phenol, bromophenol, 4,4′-sulfonyldiphenol,tert-butylphenol, biphenol, benzoic acid, salicylic acid,hydroxyisophthalic acid, phenylacetic acid, aniline, benzylamine,benzylalcohol, cinnamyl alcohol, phenylalanine, phenoxypropanol or thelike.

The naphthalene compounds having at least one hydroxy group, amino groupor carboxy group includes 1-naphthalene carboxylic acid, 2-naphthalenecarboxylic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, naphthylacetic acid, 1-hydroxy-2-naphthalene carboxylic acid,3-hydroxy-2-naphthalene carboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 6-bromo-2-hydroxynaphthalene, 2,6-naphthalenedicarboxylic acid or the like.

The anthracene compounds having at least one hydroxy group, amino groupor carboxy group in the molecule includes 9-anthracene carboxylic acid,9-hydroxymethylanthracene, 1-aminoanthracene or the like.

As the light absorbing compound, for example resins having the aromaticring structure such as benzene ring, naphthalene ring or anthracene ringin the structure, or having the hetero-aromatic ring structure such aspyridine ring, quinoline ring, thiophene ring, thiazole ring, triazinering or oxazole ring can be used.

As the light absorbing compound, resins having at least one aromaticring structure such as benzene ring, naphthalene ring or anthracene ringin the repeating structural unit can be used.

The resins having benzene ring include novolak resin, halogenatednovolak resin, polystyrene, polyhydroxystyrene or the like. In addition,resins containing benzylacrylate, benzylmethacrylate, styrene,hydroxystyrene or the like as structural unit may be mentioned. Suchresins include copolymer of benzylmethacrylate with2-hydroxypropylmethacrylate, copolymer of styrene with2-hydroxyethylmethacrylate, copolymer of hydroxystyrene withethylmethacrylate, terpolymer of benzylmethacrylate,2-hydroxypropylmethacrylate and ethylmethacrylate, terpolymer ofstyrene, 2-hydroxyethylmethacrylate and methylmethacrylate or the like.

Further, the resin having benzene ring includes the resin produced frommelamine compound (trade name: Cymel 303) and benzoguanamine compound(trade name: Cymel 1123), which is described in U.S. Pat. No. 6,323,310.

The resins having naphthalene ring or anthracene ring include forexample the resins the following structural units ((a)-(g)):

The anti-reflective coating forming composition according to the presentinvention may contain further rheology controlling agents, adhesionauxiliaries, surfactants, etc. in addition to the above described ones,if necessary.

The rheology controlling agents are added mainly aiming at increasingthe flowability of the anti-reflective coating forming composition andin particular in the baking step, increasing filling property of theanti-reflective coating forming composition into the inside of holes.Specific examples thereof include phthalic acid derivatives such asdimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexylphthalate or butyl isodecyl phthalate; adipic acid derivatives such asdi-n-butyl adipate, diisobutyl adipate, diisooctyl adipate or octyldecyladipate; maleic acid derivatives such as di-n-butyl maleate, diethylmaleate or dinonyl maleate; oleic acid derivatives such as methyloleate, butyl oleate or tetrahydrofurfuryl oleate; or stearic acidderivatives such as n-butyl stearate or glyceryl stearate. The rheologycontrolling agents are blended in proportions of usually less than 30mass % in the total composition of anti-reflective coating forlithography.

The adhesion auxiliaries are added mainly for the purpose of increasingthe adhesion between the substrate or photoresist and theanti-reflective coating forming composition, in particular preventingthe detachment of the photoresist in development. Specific examplesthereof include chlorosilanes such as trimethylchlorosilane,dimethylvinylchlorosilane, methyldiphenylchlorosilane orchloromethyidimethyl-chlorosilane; alkoxysilanes such astrimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane,dimethylvinylethoxysilane, diphenyldimethoxysilane orphenyltriethoxysilane; silazanes such as hexamethyldisilazane,N,N′-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine ortrimethylsilylimidazole; silanes such as vinyltrichlorosilane,γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxy-silane orγ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such asbenzotriazole, benzimidazole, indazole, imidazole,2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole,urazole, thiouracyl, mercaptoimidazole or mercaptopyrimidine; ureas suchas 1,1-dimethylurea or 1,3-dimethylurea, or thiourea compounds. Theadhesion auxiliaries are added in proportions of usually less than 5mass %, preferably less than 2 mass %, in the total composition of theanti-reflective coating for lithography.

The anti-reflective coating forming composition according to the presentinvention may contain surfactants with view to preventing the occurrenceof pinholes or striations and further increasing coatability not tocause surface unevenness. As the surfactants, mention may be made of,for example, nonionic surfactants such as polyoxyethylene alkyl ethers,e.g., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc.,polyoxyethylene alkyl allyl ethers, e.g., polyoxyethylene octyl phenolether, polyoxyethylene nonyl phenol ether;polyoxyethylene/polyoxypropylene block copolymers, sorbitan fatty acidesters, e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan monooleate, sorbitan trioleate, sorbitantristearate, etc.,,polyoxyethylene sorbitan fatty acid esters, e.g.,polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.; fluorinebased surfactants, e.g., EFTOP EF301, EF303, EF352 (Tochem Products Co.,Ltd.), MEGAFAC F171, F173 (Dainippon Ink and Chemicals, Inc.), FLUORADFC430, FC431 (Sumitomo 3M Limited), ASAHI GUARD AG710, SURFLON S-382,SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.),organosiloxane polymer KP341 (Shinetsu Chemical Co., Ltd.), etc. Theblending amount of the surfactants is usually 0.2 mass % or less,preferably 0.1 mass % or less, in the total composition of theanti-reflective coating for lithography according to the presentinvention. The surfactants may be added singly or two or more of themmay be added in combination.

In the present invention, as the solvents for dissolving theabove-described solid content such as polymer compounds, use may be madeof ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, propylene glycol,propylene glycol monomethyl ether, propylene glycol monomethyl etheracetate, propylene glycol propyl ether acetate, toluene, xylene, methylethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate,ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethylhydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl3-methoxypropionate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethylpyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate,etc. The organic solvents may be used singly or in combination of two ormore of them.

Further, high boiling solvents such as propylene glycol monobutyl etheror propylene glycol monobutyl ether acetate may be mixed. Among thesolvents, propylene glycol monomethyl ether, propylene glycol monomethylether acetate, ethyl lactate, butyl lactate, and cyclohexanone arepreferred for increasing the leveling property.

As photoresist to be coated as an upper layer of the anti-reflectivecoating in the present invention, any of negative type and positive typephotoresists may be used. The photoresist includes achemically-amplified type resist which consists of a photoacid generatorand a binder having a group which is decomposed with an acid andincreases alkali dissolution rate, a chemically-amplified type resistconsisting of an alkali-soluble binder, a photoacid generator, and a lowmolecular compound which is decomposed with an acid and increases thealkali dissolution rate of the resist, a chemically-amplified resistconsisting of a photoacid generator, a binder having a group which isdecomposed with an acid and increases the alkali dissolution rate, and alow molecular compound which is decomposed with an acid and increasesthe alkali dissolution rate of the resist. For example, trade name:APEX-E manufactured by Shipley Company may be mentioned. The photoresistincludes also fluorine atom-containing polymer type photoresist asdescribed in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol.3999, 357-364 (2000) or Proc. SPIE, Vol. 3999, 365-374 (2000).

As the developer for the above-mentioned positive type photoresisthaving the anti-reflective coating for lithography formed by using theanti-reflective coating forming composition of the present invention,use may be made of aqueous solutions of alkalis, e.g., inorganic alkalissuch as sodium hydroxide, potassium hydroxide, sodium carbonate, sodiumsilicate, sodium metasilicate or aqueous ammonia, primary amines such asethylamine or n-propylamine, secondary amines such as diethylamine ordi-n-butylamine, tertiary amines such as triethylamine ormethyidiethylamine, alcohol amines such as dimethylethanolamine ortriethanolamine, quaternary ammonium salts such as tetramethylammoniumhydroxide, tetraethylammonium hydroxide or choline, cyclic amines suchas pyrrole or piperidine, etc. Furthermore, a suitable amount ofalcohols such as isopropyl alcohol or surfactants such as nonionicsurfactant can be added to the aqueous solution of above-describedalkalis. Among these, a preferred developer includes quaternary ammoniumsalts, more preferably tetramethylammonium hydroxide and choline.

Now, the method fofororming photoresist patterns will be described. On asubstrate for use in the production of precision integrated circuitelement (silicon/silicon dioxide coat substrate, silicon nitridesubstrate, glass substrate, ITO substrate or the like), ananti-reflective coating forming composition is coated by a suitablecoating method, for example, with a spinner, a coater or the like, andthereafter the substrate is baked to cure the composition to fabricatean anti-reflective coating. The film thickness of the anti-reflectivecoating is for example 0.01 to 3.0 μm, or for example 0.03 to 1.0 μm.The conditions of baking after the coating are for example 80 to 250° C.for 0.5 to 120 minutes, or for example 150 to 250° C. for 0.5 to 10minutes. Then, a photoresist is coated, it is exposed to light through apredetermined mask, developed, rinsed and dried to obtain a goodphotoresist pattern. If necessary, post exposure bake (PEB) may beperformed. In addition, it is able to form a desired pattern on thesubstrate by removing by dry etching a part of the anti-reflectivecoating which a photoresist was removed by development in the previousstep.

The anti-reflective coating produced from the composition for forminganti-reflective coating according to the present invention in which atriazine trione compound having hydroxyalkyl structure as substituent onnitrogen atom, a triazine trione oligomer compound having hydroxyalkylstructure as substituent on nitrogen atom, or a triazine trione polymercompound having hydroxyalkyl structure as substituent on nitrogen atomis contained has a property of absorbing efficiently irradiation lightwith a wavelength of 248 nm, 193 nm or 157 nm. Therefore, the coatingexerts an excellent effect of preventing reflection light from asubstrate, and thus a photoresist pattern being an upper layer can besatisfactorily formed. In addition, the anti-reflective coating producedfrom the composition for forming anti-reflective coating according tothe present invention in which a triazine trione compound havinghydroxyalkyl structure as substituent on nitrogen atom, a triazinetrione oligomer compound having hydroxyalkyl structure as substituent onnitrogen atom, or a triazine trione polymer compound having hydroxyalkylstructure as substituent on nitrogen atom is contained has a relativelyhigh dry etching rate owing to inclusion of triazine trione ring havingmany hetero atoms (nitrogen atom, oxygen atom).

In the addition, light absorption characteristics, attenuationcoefficient, refractive index and the like of the anti-reflectivecoating to irradiation light used can be controlled by the selection ofM moiety contained in the compound of formula (1) or the selection ofthe structure of Ar moiety contained in the substitute of formula (2) orthe linking group of formula (4), that is, the selection of ringstructure such as benzene ring, naphthalene ring or anthracene ring andthe kind and number of substituent on the ring.

The anti-reflective coating formed from the anti-reflective coatingforming composition according to the present invention has anattenuation coefficient k to a light at a wavelength of 248 nm rangingfrom 0.40 to 0.65, or 0.40 to 0.60, or 0.45 to 0.65, or to a light at awavelength of 193 nm ranging from 0.20 to 0.60, or 0.25 to 0.60. And,the anti-reflective coating has an attenuation coefficient k to a lightat a wavelength of 157 nm ranging from 0.20 to 0.50 or 0.30 to 0.45 or0.30 to 0.40.

The anti-reflective coating formed from the composition for forminganti-reflective coating according to the present invention can be useddepending on process condition as a coating having the followingfunctions: a function of preventing reflection light, a function ofpreventing a mutual interaction between a substrate and a photoresist, afunction of preventing an adverse effect to a substrate by a materialused in the photoresist or a substance generated on exposure to thephotoresist, or a function of preventing an adverse effect to aphotoresist by a substance generated from the substrate on exposure tolight or heating.

Hereinafter, the present invention will be described based on examplesand comparative examples but the present invention is not limitedthereto.

SYNTHESIS EXAMPLE 1

After 5.0 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 4.8 g of6-hydroxy-2-naphthalene carboxylic acid and 0.02 g of benzyltriethylammonium chloride were dissolved in 39 g of propylene glycol monomethylether, the resulting solution was reacted at 130° C. for 24 hours toobtain an oligomer compound solution. The resulting oligomer compoundwas subjected to GPC analysis and had a weight average molecular weightof 3400 in terms of standard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (35) and oligomer compound in which triazinetrione rings are linked through linking group of formula (52).

SYNTHESIS EXAMPLE 2

After 4.0 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 6.1 g of6-hydroxy-2-naphthalene carboxylic acid and 0.02 g of benzyltriethylammonium chloride were dissolved in 42 g of propylene glycol monomethylether, the resulting solution was reacted at 130° C. for 24 hours toobtain an oligomer compound solution. The resulting oligomer compoundwas subjected to GPC analysis and had a weight average molecular weightof 1700 in terms of standard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (35) and oligomer compound in which triazinetrione rings are linked through linking group of formula (52).

SYNTHESIS EXAMPLE 3

After 4.0 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 7.2 g of6-hydroxy-2-naphthalene carboxylic acid and 0.02 g of benzyltriethylammonium chloride were dissolved in 45 g of propylene glycol monomethylether, the resulting solution was reacted at 130° C. for 24 hours toobtain an oligomer compound solution. The resulting oligomer compoundwas subjected to GPC analysis and had a weight average molecular weightof 1200 in terms of standard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (35) and oligomer compound in which triazinetrione rings are linked through linking group of formula (52).

SYNTHESIS EXAMPLE 4

After 1.7 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 3.4 g of6-hydroxy-2-naphthalene carboxylic acid and 0.09 g of benzyltriethylammonium chloride were dissolved in 20 g of propylene glycol monomethylether, the resulting solution was reacted at 130° C. for 24 hours toobtain an oligomer compound solution. The resulting oligomer compoundwas subjected to GPC analysis and had a weight average molecular weightof 1200 in terms of standard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (35) and oligomer compound in which triazinetrione rings are linked through linking group of formula (52).

SYNTHESIS EXAMPLE 5

After 21 g of glycidylmethacrylate and 39 g of2-hydroxypropylmethacrylate were dissolved in 242 g of propylene glycolmonomethyl ether, the temperature of the resulting solution was raisedto 70° C., and then 0.6 g of azobisisobutyronitrile was added theretowhile the reaction solution was kept at 70° C., and the resultingsolution was reacted at 70° C. for 24 hours to obtain a solution ofcopolymerized polymer compound of glycidylmethacrylate and2-hydroxypropylmethacrylate. The resulting polymer compound wassubjected to GPC analysis and had a weight average molecular weight of50000 in terms of standard polystyrene.

To 100 g of a solution containing 20 g of the copolymerized polymercompound, 10 g of 9-anthracene carboxylic acid, 0.3 g ofbenzyltriethylammonium chloride and 41 g of propylene glycol monomethylether were added, and the resulting solution was reacted at 130° C. for24 hours to obtain a compound of formula (60). In formula (60), m is amolar ratio of constitutional unit, and n+m=1.

SYNTHESIS EXAMPLE 6

After 0.70 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 2.44 g of2,4,6-tribromo-3-hydroxy benzoic acid and 0.04 g of benzyltriethylammonium chloride were dissolved in 12.72 g of propylene glycolmonomethyl ether, the atmosphere was replaced with nitrogen and then theresulting solution was reacted at 125° C. for 24 hours to obtain anoligomer compound solution. The resulting oligomer compound wassubjected to GPC analysis and had a weight average molecular weight of1300 in terms of standard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (30) and oligomer compound in which triazinetrione rings are linked through linking group of formula (45).

SYNTHESIS EXAMPLE 7

After 2.0 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 6.70 g of3,5-diiodo-2-hydroxy benzoic acid and 0.115 g of benzyltriethyl ammoniumchloride were dissolved in 35.25 g of propylene glycol monomethyl ether,the atmosphere was replaced with nitrogen and then the resultingsolution was reacted at 125° C. for 24 hours to obtain an oligomercompound solution. The resulting oligomer compound was subjected to GPCanalysis and had a weight average molecular weight of 2000 in terms ofstandard polystyrene.

In the meanwhile, it is assumed that the oligomer compound obtained inthis Synthesis Example contains triazine trione compound havingsubstituent of formula (32) and oligomer compound in which triazinetrione rings are linked through linking group of formula (46).

SYNTHESIS EXAMPLE 8

After 2.0 g of monoallyldiglycidyl isocyanuric acid and 1.2 g ofmonoallyl isocyanuric acid were dissolved in 13.2 g of cyclohexanone,the temperature of the reaction solution was raised to 120° C., andsimultaneously nitrogen was flushed. Thereafter, 0.08 g ofbenzyltriethyl ammonium chloride as catalyst was added thereto, and theresulting mixture was stirred under nitrogen atmosphere for 21 hours.The resulting reaction product was subjected to GPC analysis and had aweight average molecular weight of 5800 in terms of standardpolystyrene.

In the meanwhile, it is assumed that the reaction product obtained inthis Synthesis Example contains a compound having the constitutionalunit of formula (61).

SYNTHESIS EXAMPLE 9

After 2.0 g of monoallyidiglycidyl isocyanuric acid and 1.5 g ofmonophenyl isocyanuric acid were dissolved in 14.2 g of cyclohexanone,the temperature of the reaction solution was raised to 120° C., andsimultaneously nitrogen was flushed. Thereafter, 0.08 g ofbenzyltriethyl ammonium chloride as catalyst was added thereto, and theresulting mixture was stirred under nitrogen atmosphere for 19 hours.The resulting reaction product was subjected to GPC analysis and had aweight average molecular weight of 2400 in terms of standardpolystyrene.

In the meanwhile, it is assumed that the reaction product obtained inthis Synthesis Example contains a compound having the constitutionalunit of formula (62).

SYNTHESIS EXAMPLE 10

After 2.0 g of monoallyldiglycidyl isocyanuric acid and 1.0 g ofmonomethyl isocyanuric acid were dissolved in 12.4 g of cyclohexanone,the temperature of the reaction solution was raised to 120° C., andsimultaneously nitrogen was flushed. Thereafter, 0.08 g ofbenzyltriethyl ammonium chloride as catalyst was added thereto, and theresulting mixture was stirred under nitrogen atmosphere for 19 hours toobtain a solution containing a reaction product.

In the meanwhile, it is assumed that the reaction product obtained inthis Synthesis Example contains a compound having the constitutionalunit of formula (63).

SYNTHESIS EXAMPLE 11

After 2.0 g of monoallyldiglycidyl isocyanuric acid and 2.2 g ofmonomethyldicarboxybutyl isocyanurate were dissolved in 17.4 g ofcyclohexanone, the temperature of the reaction solution was raised to11324 20° C., and simultaneously nitrogen was flushed. Thereafter, 0.08g of benzyltriethyl ammonium chloride as catalyst was added thereto, andthe resulting mixture was stirred under nitrogen atmosphere for 19hours. The resulting reaction product was subjected to GPC analysis andhad a weight average molecular weight of 12200 in terms of standardpolystyrene.

In the meanwhile, it is assumed that the reaction product obtained inthis Synthesis Example contains a compound having the constitutionalunit of formula (64).

SYNTHESIS EXAMPLE 12

After 0.50 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.) and 1.2 g ofmonocarboxypropyldimethyl isocyanurate were dissolved in 7.0 g ofdimethylformamide, the temperature of the reaction solution was raisedto 120° C. and simultaneously nitrogen was flushed to the reactionsolution. Thereafter, 0.03 g of benzyltriethyl ammonium chloride ascatalyst was added thereto, and the resulting mixture was stirred undernitrogen atmosphere for 20 hours to obtain a solution containing areaction product of formula (65).

SYNTHESIS EXAMPLE 13

After 1.8 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.) and 4.0 g ofmonocarboxymethyl dimethyl isocyanurate were dissolved in 23.8 g ofcyclohexanone, the temperature of the reaction solution was raised to120° C. and simultaneously nitrogen was flushed to the reactionsolution. Thereafter, 0.1 g of benzyltriethyl ammonium chloride ascatalyst was added thereto, and the resulting mixture was stirred undernitrogen atmosphere for 20 hours to obtain a solution containing areaction product of formula (66).

SYNTHESIS EXAMPLE 14

10 g of cresol novolak resin (trade name: ECN 1299 manufactured by AsahiChiba Co., Ltd., weight average molecular weight: 3900) was added to 80g of propylene glycol monomethyl ether, and dissolved therein. To thesolution, 9.7 g of 9-anthracene carboxylic acid and 0.26 g ofbenzyltriethyl ammonium chloride were added and the resulting solutionwas reacted at 105° C. for 24 hours to obtain a resin compound offormula (67). The resulting resin compound was subjected to GPC analysisand had a weight average molecular weight of 5600 in terms of standardpolystyrene.

SYNTHESIS EXAMPLE 15

After 6.8 g of tris-(2,3-epoxypropyl)-isocyanurate (trade name: TEPICmanufactured by Nissan Chemical Industries, Ltd.), 12.9 g of3,7-dihydroxy-2-naphthalene carboxylic acid and 0.37 g of benzyltriethylammonium chloride were dissolved in 80 g of cyclohexanone, the resultingsolution was reacted at 130° C. for 24 hours to obtain an oligomercompound solution. The resulting oligomer compound was subjected to GPCanalysis and had a weight average molecular weight of 1400 in terms ofstandard polystyrene. In the meanwhile, it is assumed that the oligomercompound obtained in this Synthesis Example contains triazine trionecompound having substituent of formula (37) and oligomer compound inwhich triazine trione rings are linked through linking group of formula(53).

SYNTHESIS EXAMPLE 16

After 30 g of trifluoroethylmethacrylate, 12.3 g of methacrylic acid and4.6 g of 2-hydroxypropylmethacrylate were dissolved in 201 g ofpropylene glycol monomethyl ether, the temperature of the resultingsolution was raised to 60° C., and then 3.3 g of2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) was added thereto whilethe reaction solution was kept at 60° C., and the reaction solution wasreacted at 60° C. for 24 hours. The reaction solution was added dropwiseto a mixed solvent of water and ethanol, and the precipitate separatedout was filtered off to obtain a copolymerized polymer compound oftrifluoroethylmethacrylate, methacrylic acid and2-hydroxypropylmethacrylate. The resulting polymer compound wassubjected to GPC analysis and had a weight average molecular weight of15000 in terms of standard polystyrene.

SYNTHESIS EXAMPLE 17

After 30 g of trichloroethylmethacrylate and 4.5 g of2-hydroxypropylmethacrylate were dissolved in 145 g of propylene glycolmonomethyl ether, the temperature of the resulting solution was raisedto 60° C., and then 1.7 g of2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) was added thereto whilethe reaction solution was kept at 60° C., and the reaction solution wasreacted at 60° C. for 24 hours. The reaction solution was added dropwiseto a mixed solvent of water and ethanol, and the precipitate separatedout was filtered off to obtain a copolymerized polymer compound oftrichloroethylmethacrylate and 2-hydroxypropylmethacrylate. Theresulting polymer compound was subjected to GPC analysis and had aweight average molecular weight of 11000 in terms of standardpolystyrene.

SYNTHESIS EXAMPLE 18

After 21 g of glycidylmethacrylate and 39 g of2-hydroxypropylmethacrylate were dissolved in 242 g of propylene glycolmonomethyl ether, the temperature of the resulting solution was raisedto 70° C., and then 0.6 g of azobisisobutyronitrile was added theretowhile the reaction solution was kept at 70° C. Then, the reactionsolution was reacted at 70° C. for 24 hours to obtain a solution ofcopolymerized polymer compound of glycidylmethacrylate and2-hydroxypropylmethacrylate. The resulting polymer compound wassubjected to GPC analysis and had a weight average molecular weight of50000 in terms of standard polystyrene. To 100 g of a solutioncontaining 20 g of the polymer compound, 10 g of 9-anthracenecarboxylicacid, 0.3 g of benzyltriethyl ammonium chloride and 41 g of propyleneglycol monomethyl ether were added, the resulting solution was reactedat 130° C. for 24 hours to a solution of polymer compound of formula(68).

EXAMPLE 1

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 1, 0.3 g of hexamethoxymethylmelamine (trade name:Cymel 303; manufactured by Mitsui Cytec Co., Ltd.) and 0.03 g ofpyridinium-p-toluenesulfonic acid were mixed, and the resulting mixturewas dissolved in 20 g of propylene glycol monomethyl ether and 28 g ofethyl lactate to obtain a solution. Then, the solution was filteredthrough a micro filter made of polyethylene having a pore diameter of0.10 μm, and then, the solution was filtered through a micro filter madeof polyethylene having a pore diameter of 0.05 μm, to prepare acomposition solution for forming anti-reflective coating.

EXAMPLE 2

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 2, 0.3 g of hexamethoxymethylmelamine (trade name:Cymel 303; manufactured by Mitsui Cytec Co., Ltd.) and 0.03 g ofpyridinium-p-toluenesulfonic acid were mixed, and the resulting mixturewas dissolved in 20 g of propylene glycol monomethyl ether and 28 g ofethyl lactate to obtain a solution. Then, the solution was filteredthrough a micro filter made of polyethylene having a pore diameter of0.10 μm, and then, the solution was filtered through a micro filter madeof polyethylene having a pore diameter of 0.05 μm, to prepare acomposition solution for forming anti-reflective coating.

EXAMPLE 3

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 3, 0.3 g of hexamethoxymethylmelamine (trade name:Cymel 303; manufactured by Mitsui Cytec Co., Ltd.) and 0.03 g ofpyridinium-p-toluenesulfonic acid were mixed, and the resulting mixturewas dissolved in 20 g of propylene glycol monomethyl ether and 28 g ofethyl lactate to obtain a solution. Then, the solution was filteredthrough a micro filter made of polyethylene having a pore diameter of0.10 pm, and then, the solution was filtered through a micro filter madeof polyethylene having a pore diameter of 0.05 μm, to prepare acomposition solution for forming anti-reflective coating.

EXAMPLE 4

To 10 g of a solution containing 2 g of the polymer compound obtained inSynthesis Example 4, 0.5 g of tetramethoxymethyl glycol uril (tradename: Powderlink 1174; manufactured by Mitsui Cytec Co., Ltd.) and 0.05g of pyridinium-p-toluenesulfonic acid were mixed, and the resultingmixture was dissolved in 23 g of propylene glycol monomethyl ether and31 g of ethyl lactate to obtain a solution. Then, the solution wasfiltered through a micro filter made of polyethylene having a porediameter of 0.10 μm, and then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.05 μm, toprepare a composition solution for forming anti-reflective coating.

EXAMPLE 5

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 6, 0.5 g of tetramethoxymethyl glycol uril and 0.05g of pyridinium-p-toluenesulfonic acid were mixed, and 56.7 g ofpropylene glycol monomethyl ether was added thereto to obtain asolution. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLE 6

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 7, 0.5 g of tetramethoxymethyl glycol uril and 0.05g of pyridinium-p-toluenesulfonic acid were mixed, and 56.7 g ofpropylene glycol monomethyl ether was added thereto to obtain asolution. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLE 7

To 6 g of a solution containing 1.2 g of the reaction product obtainedin Synthesis Example 8, 0.3 g of hexamethoxymethylmelamine and 0.03 g ofp-toluenesulfonic acid were mixed, and 23.7 g of ethyl lactate was addedthereto. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLES 8 TO 12

Similarly to the above-mentioned procedure, to 6 g of a solutioncontaining 1.2 g of the reaction product obtained in Synthesis Examples9 to 13, 0.3 g of hexamethoxymethylmelamine and 0.03 g ofp-toluenesulfonic acid were mixed, and 23.7 g of ethyl lactate was addedthereto. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLE 13

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.5 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.05 g ofpyridinium-p-toluenesulfonic acid, 20 g of propylene glycol monomethylether, 59 g of ethyl lactate and 12 g of cyclohexanone were added toobtain a solution. Then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.10 μm, and then,the solution was filtered through a micro filter made of polyethylenehaving a pore diameter of 0.05 μm, to prepare a composition solution forforming anti-reflective coating.

EXAMPLE 14

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.4 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.1 g ofhexamethoxymethylmelamine (trade name: Cymel 303; manufactured by MitsuiCytec Co., Ltd.), 0.05 g of pyridinium-p-toluenesulfonic acid, 16 g ofpropylene glycol monomethyl ether, 49 g of ethyl lactate and 8 g ofcyclohexanone were added to obtain a solution. Then, the solution wasfiltered through a micro filter made of polyethylene having a porediameter of 0.10 μm, and then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.05 μm, toprepare a composition solution for forming anti-reflective coating.

EXAMPLE 15

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.3 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.2 g ofhexamethoxymethylmelamine (trade name: Cymel 303; manufactured by MitsuiCytec Co., Ltd.), 0.05 9 of pyridinium-p-toluenesulfonic acid, 16 g ofpropylene glycol monomethyl ether, 49 g of ethyl lactate and 8 g ofcyclohexanone were added to obtain a solution. Then, the solution wasfiltered through a micro filter made of polyethylene having a porediameter of 0.10 μm, and then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.05 μm, toprepare a composition solution for forming anti-reflective coating.

EXAMPLE 16

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 2.0 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.2 g ofpyridinium-p-toluenesulfonic acid, 14 g of propylene glycol monomethylether, 43 g of ethyl lactate and 6 g of cyclohexanone were added toobtain a solution. Then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.10 μm, and then,the solution was filtered through a micro filter made of polyethylenehaving a pore diameter of 0.05 μm, to prepare a composition solution forforming anti-reflective coating.

EXAMPLE 17

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.5 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.05 g of5-sulfosalicylic acid, 12 9 of propylene glycol monomethyl ether, 37 gof ethyl lactate and 4 g of cyclohexanone were added to obtain asolution. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLE 18

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.5 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.09 g ofdinonylnaphthalene sulfonate, 12 g of propylene glycol monomethyl ether,37 g of ethyl lactate and 4 g of cyclohexanone were added to obtain asolution. Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

EXAMPLE 19

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 2.0 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.05 g ofpyridinium-p-toluenesulfonic acid, 0.09 g of the polymer compoundobtained in Synthesis Example 16, 10 g of propylene glycol monomethylether, 30 g of ethyl lactate and 2 g of cyclohexanone were added toobtain a solution. Then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.10 μm, and then,the solution was filtered through a micro filter made of polyethylenehaving a pore diameter of 0.05 μm, to prepare a composition solution forforming anti-reflective coating.

EXAMPLE 20

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.5 g of tetrabutoxymethyl glycol uril (tradename: Cymel 1170; manufactured by Mitsui Cytec Co., Ltd.), 0.05 g ofpyridinium-p-toluenesulfonic acid, 0.18 g of the polymer compoundobtained in Synthesis Example 17, 10 g of propylene glycol monomethylether, 30 g of ethyl lactate and 2 g of cyclohexanone were added toobtain a solution. Then, the solution was filtered through a microfilter made of polyethylene having a pore diameter of 0.10 μm, and then,the solution was filtered through a micro filter made of polyethylenehaving a pore diameter of 0.05 μm, to prepare a composition solution forforming anti-reflective coating.

EXAMPLE 21

To 10 g of a solution containing 2 g of the oligomer compound obtainedin Synthesis Example 15, 0.8 g of tris-(2,3-epoxypropyl)-isocyanurate(trade name: TEPIC manufactured by Nissan Chemical Industries, Ltd.), 39g of propylene glycol monomethyl ether and 47 g of propylene glycolmonomethylether acetate were added to obtain a solution. Then, thesolution was filtered through a micro filter made of polyethylene havinga pore diameter of 0.10 μm, and then, the solution was filtered througha micro filter made of polyethylene having a pore diameter of 0.05 μm,to prepare a composition solution for forming anti-reflective coating.

COMPARATIVE EXAMPLE 1

To 10 g of a solution containing 2 g of the polymer compound obtained inSynthesis Example 5, 0.5 g of tetramethoxymethyl glycol uril (tradename: Powderlink 1174; manufactured by Mitsui Cytec Co., Ltd.) and 0.03g of p-toluenesulfonic acid were mixed. The resulting solution wasdissolved in 37.3 g of propylene glycol monomethyl ether and 19.4 g ofcyclohexanone to obtain a solution. Then, the solution was filteredthrough a micro filter made of polyethylene having a pore diameter of0.10 μm, and then, the solution was filtered through a micro filter madeof polyethylene having a pore diameter of 0.05 μm, to prepare acomposition solution for forming anti-reflective coating.

COMPARATIVE EXAMPLE 2

To 10 9 of a solution containing 2 g of the resin obtained in SynthesisExample 14, 0.53 g of hexamethoxymethylmelamine and 0.05 g ofp-toluenesulfonic acid monohydrate were mixed. The resulting solutionwas dissolved in 14.3 g of ethyl lactate, 1.13 g of propylene glycolmonomethyl ether and 2.61 g of cyclohexanone to obtain 9% solution.Then, the solution was filtered through a micro filter made ofpolyethylene having a pore diameter of 0.10 μm, and then, the solutionwas filtered through a micro filter made of polyethylene having a porediameter of 0.05 μm, to prepare a composition solution for forminganti-reflective coating.

COMPARATIVE EXAMPLE 3

To 10 g of a solution containing 2 g of the polymer compound obtained inSynthesis Example 18, 0.3 g of hexamethoxymethylmelamine, 0.01 g ofp-toluenesulfonic acid, 37.3 g of propylene glycol monomethyl ether and19.4 g of propylene glycol monomethyl ether acetate were added to obtaina solution. Then, the solution was filtered through a micro filter madeof polyethylene having a pore diameter of 0.10 μm, and then, thesolution was filtered through a micro filter made of polyethylene havinga pore diameter of 0.05 μm, to prepare a composition solution forforming anti-reflective coating.

Dissolution Test in Solvent for Photoresist

The composition solutions for forming anti-reflective coating obtainedin Examples 1 to 21 and Comparative Examples 1 to 3 were coated onsilicon wafers by means of a spinner. The coated silicon wafers wereheated at 205° C. for 1 minute on a hot plate to form anti-reflectivecoatings (film thickness 0.10 μm). The anti-reflective coatings weredipped in a solvent used for resists, for example ethyl lactate andpropylene glycol monomethyl ether and as a result it was confirmed thatthe resulting coatings were insoluble in these solvents.

Test of Intermixing with Photoresist

The composition solutions for forming anti-reflective coating obtainedin Examples 1 to 6, 13 to 21 and Comparative Examples 1 and 3 werecoated on silicon wafers by means of a spinner. The coated siliconwafers were heated at 205° C. for 1 minute on a hot plate to formanti-reflective coatings (film thickness 0.10 μm). On eachanti-reflective coating was coated a commercially available photoresistsolution (manufactured by Shipley Company; trade name: UV113, etc.) bymeans of a spinner. The coated wafers were heated at 120° C. for 1minute on a hot plate. After exposure of the resists to light, postexposure bake (PEB) was performed at 115° C. for 1.5 minute. Afterdeveloping the photoresists, the film thickness of the anti-reflectivecoatings was measured and it was confirmed that no intermixing occurredbetween the anti-reflective coatings for lithography obtained fromanti-reflective coating solutions prepared in Examples 1 to 6, 13 to 21and Comparative Examples 1 and 3 and the photoresist layers.

Similarly, on each anti-reflective coating (film thickness 0.23 μm)formed from the composition solutions for forming anti-reflectivecoating obtained in Examples 7 to 9 and Comparative Example 2 was coateda commercially available photoresist solution (manufactured by SumitomoChemical Co., Ltd.; trade name: PAR710) by means of a spinner. Thecoated wafers were heated at 90° C. for 1 minute on a hot plate. Afterexposure of the resists to light, post exposure bake (PEB) was performedat 90° C. for 1.5 minute. After developing the photoresists, the filmthickness of the anti-reflective coatings was measured and it wasconfirmed that no intermixing occurred between the anti-reflectivecoatings obtained from anti-reflective coating solutions prepared inExamples 7 to 9 and Comparative Example 2 and the photoresist layers.

Test on Optical Parameter

The composition solutions for forming anti-reflective coating obtainedin Examples 1 to 4, 13 to 21 and Comparative Examples 1 and 3 werecoated on silicon wafers by means of a spinner. The coated siliconwafers were heated at 205° C. for 1 minute on a hot plate to formanti-reflective coatings (film thickness 0.06 μm). On eachanti-reflective coating, refractive index (n) and attenuationcoefficient (k) at a wavelength of 248 nm were measured with aspectroscopic ellipsometer. The results of the measurement are shown inTables 2 and 5.

The composition solutions for forming anti-reflective coating obtainedin Examples 5 and 6 were coated on silicon wafers by means of a spinner.The coated silicon wafers were heated at 205° C. for 1 minute on a hotplate to form anti-reflective coatings (film thickness 0.06 μm). On eachanti-reflective coating, refractive index (n) and attenuationcoefficient (k) at a wavelength of 157 nm were measured with aspectroscopic ellipsometer (manufactured by J. A. Woollam Co., VUV-VASEVU-302). The results of the measurement are shown in Table 3.

The composition solutions for forming anti-reflective coating obtainedin Examples 7 to 12 and Comparative Example 2 were coated on siliconwafers by means of a spinner. The coated silicon wafers were heated at205° C. for 1 minute on a hot plate to form anti-reflective coatings(film thickness 0.09 μm). On each anti-reflective coating, refractiveindex (n) and attenuation coefficient (k) at a wavelength of 193 nm weremeasured with a spectroscopic ellipsometer. The results of themeasurement are shown in Table 4.

Measurement of Dry Etching Rate

The composition solutions for forming anti-reflective coating obtainedin Examples 1 to 21 and Comparative Examples 1 to 3 were coated onsilicon wafers by means of a spinner. The coated silicon wafers werebaked at 205° C. for 1 minute on a hot plate to form anti-reflectivecoatings. Then, dry etching rate on each anti-reflective coating wasmeasured with RIE system ES401 manufactured by Nippon Scientific Co.,Ltd. under the condition in which CF was used as dry etching gas.

Similarly, a photoresist solution (trade name: UV113 manufactured byShipley Company and trade name: PAR710 manufactured by Sumitomo ChemicalCo., Ltd.) was coated on silicon wafers by means of a spinner. Then, dryetching rate on each photoresist was measured with RIE system ES401manufactured by Nippon Scientific Co., Ltd. under the condition in whichCF was used as dry etching gas. The dry etching rate on theanti-reflective coatings in Examples 1 to 4, 13 to 21 and ComparativeExamples 1 and 3 was compared with that on the photoresist (trade name:UV113) manufactured by Shipley Company. The results of the measurementare shown in Tables 2 and 5. The dry etching rate on the anti-reflectivecoatings in Examples 5 to 12 and Comparative Example 2 was compared withthat on the photoresist (trade name: PAR710) manufactured by SumitomoChemical Co., Ltd. The results of the measurement are shown in Tables 3and 4.

Simulation of the First Minimum Film Thickness

The first minimum film thickness and the reflection rate in case wherean anti-reflective coating was used in the first minimum film thicknesswere determined by simulation calculation with the refractive index (n)and the attenuation coefficient (k) at a wavelength of 248 nm of theanti-reflective coatings for lithography prepared from the compositionsolutions for forming anti-reflective coating obtained in Examples 1 to4, 13 to 21 and Comparative Examples 1 and 3. In this case, for thesimulation PROLITH/2 manufactured by FINLE Technologies Inc. was used.The results are shown in Tables 2 and 5.

TABLE 2 First minimum Refractive Attenuation film Reflection indexcoefficient thickness rate Selection (n) (k) (nm) (%) ratio* Example 11.80 0.50 41 <0.1 1.4 Example 2 1.80 0.52 41 <0.1 1.3 Example 3 1.790.54 41 <0.1 1.3 Example 4 1.81 0.50 41 <0.1 1.5 Compar- 1.48 0.47 590.2 1.3 ative Example 1 *“Section ratio” means dry etching rateselection ratio to photoresist.

TABLE 3 Refractive Attenuation Dry etching rate selection index (n)coefficient (k) ratio to photoresist Example 5 1.75 0.36 2.47 Example 61.61 0.41 2.08

TABLE 4 Refractive Attenuation Dry etching rate selection index (n)coefficient (k) ratio to photoresist Example 7 2.03 0.44 1.85 Example 81.95 0.59 1.60 Example 9 2.03 0.48 2.04 Example 10 1.97 0.29 1.85Example 11 1.96 0.28 2.08 Example 12 1.99 0.27 2.45 Comparative 1.600.47 0.88 Example 2

TABLE 5 First Atten- minimum Refractive uation film Reflection indexcoefficient thickness rate Selection (n) (k) (nm) (%) ratio* Example 131.82 0.59 39 <1 1.4 Example 14 1.82 0.61 38 <1 1.4 Example 15 1.84 0.6138 <1 1.4 Example 16 1.77 0.45 44 <1 1.6 Example 17 1.80 0.58 40 <1 1.4Example 18 1.81 0.57 40 <1 1.4 Example 19 1.79 0.59 42 <1 1.4 Example 201.79 0.57 42 <1 1.4 Example 21 1.82 0.59 39 <1 1.5 Comparative 1.50 0.4857 <1 1.3 Example 3 *“Section ratio” means dry etching rate selectionratio to photoresist.

From the above-mentioned results, it is understood that theanti-reflective coatings prepared from the composition for forminganti-reflective coating according to the present invention have asatisfactorily effective refractive index and attenuation coefficientfor a light of a wavelength of 248 nm (Examples 1 to 4 and 13 to 21), awavelength of 157 nm (Examples 5 and 6), and a wavelength of 193 nm(Examples 7 to 12).

In addition, it is understood that they have a high selection ratio ofdry etching rate to photoresist (Examples 1 to 21). Further, it isunderstood that they exerts a high protection effect against lightreflection compared with the prior anti-reflective coating, and thatthey can be used in thinner film (Comparison between Examples 1 to 4 andComparative Example 1, and between Examples 13 to 21 and ComparativeExample 3). Consequently, it is concluded that the composition accordingto the present invention makes possible to reduce the time required forremoval of anti-reflective coatings by dry etching, therefore it canprevent adverse phenomenon that film thickness of photoresist would bereduced with the removal of anti-reflective coatings by dry etching.

As mentioned above, the present invention can provide an anti-reflectivecoating forming composition for forming an excellent bottom organicanti-reflective coating that has a good absorption of light at awavelength utilized for manufacturing a semiconductor device, thatexerts a high protection effect against light reflection, that has ahigh dry etching rate compared with the photoresist layer, that causesno intermixing with the photoresist layer, and that occurs no diffusionto the photoresist upon heating and drying.

1. A composition for forming anti-reflective coating characterized inthat the composition comprises a triazine trione oligomer compoundhaving hydroxyalkyl structure as substituent on nitrogen atom, atriazine trione polymer compound having hydroxyalkyl structure assubstituent on nitrogen atom or a mixture thereof; wherein the triazinetrione oligomer compound having hydroxyalkyl structure as substituent onnitrogen atom, or the triazine trione polymer compound havinghydroxyalkyl structure as substituent on nitrogen atom is a triazinetrione oligomer compound, triazine trione polymer compound, or mixturethereof having a structure in which at least two triazine trione ringsare linked through a linking group of formula (4) or (5) on the nitrogenatoms:

wherein A₁, A₂ and A₃ are independently of one another hydrogen atom,methyl or ethyl, each Y is independently a direct bond or —C(═O)—, Ar isbenzene ring or naphthalene ring which may be substituted with C₁₋₆alkyl, phenyl, naphthyl, halogen atom, C₁₋₆ alkoxycarbonyl, nitro,carboxy, cyano, C₁₋₆ alkoxy, hydroxy, thiol, C₁₋₆ alkylthio or amino, Qis C₁₋₆ alkyl, C₅₋₈ cycloalkyl, Ar or —CH₂—Ar—CH₂—, R₁ is C₁₋₆ alkyl,phenyl or benzyl, R₂ is hydrogen atom, C₁₋₆ alkyl, phenyl or benzyl. 2.The composition for forming anti-reflective coating according to claim1, wherein the triazine trione oligomer compound, triazine trionepolymer compound, or mixture thereof having a structure in which atleast two triazine trione rings are linked through a linking group offormula (4) or (5) on the nitrogen atoms has a structure of formula (8)or (9):


3. The composition for forming anti-reflective coating according toclaim 1, wherein the triazine trione oligomer compound, triazine trionepolymer compound, or mixture thereof having a structure in which atleast two triazine trione rings are linked through a linking group offormula (4) on the nitrogen atoms is produced from a triazine trionecompound having at least two nitrogen atoms having a substituent offormula (13) on nitrogen atom and a phenyl compound or naphthalenecompound of formula (14) having at least two substituents selected fromcarboxy and hydroxy which are identical or different from each other.


4. The composition for forming anti-reflective coating according toclaim 3, wherein the phenyl compound or naphthalene compound of formula(14) is at least one compound selected from the group consisting ofcompounds of formulae (16) to (21)

wherein B is hydrogen atom, C₁₋₆ alkyl, phenyl, naphthyl, halogen atom,C₁₋₆ alkoxycarbonyl, nitro, carboxy, cyano, C₁₋₆ alkoxy, hydroxy, thiol,C₁₋₆ alkylthio or amino, n is a number of 1 to 6, m is a number of 1 to4, and B may be identical with or different from each other in casewhere n or m is 2 or more.
 5. The composition for forminganti-reflective coating according to claim 1, further containing acrosslinking agent having at least two crosslink-forming substituents.6. The composition for forming anti-reflective coating according toclaim 1, further containing an acid and/or an acid generator.
 7. Thecomposition for forming anti-reflective coating according to claim 1,further containing a resin having at least one crosslinking-formingsubstituent selected from hydroxy, carboxy, amino and thiol.
 8. Ananti-reflective coating produced by coating the composition for forminganti-reflective coating according to claim 1 on a semiconductorsubstrate, and baking it, wherein the anti-reflective coating has anattenuation coefficient k to a light at a wavelength of 248 nm rangingfrom 0.40 to 0.65.
 9. An anti-reflective coating produced by coating thecomposition for forming anti-reflective coating according to claim 1 ona semiconductor substrate, and baking it, wherein the anti-reflectivecoating has an attenuation coefficient k to a light at a wavelength of157 nm ranging from 0.20 to 0.50.
 10. An anti-reflective coatingproduced by coating the composition for forming anti-reflective coatingaccording to claim 1 on a semiconductor substrate, and baking it,wherein the anti-reflective coating has an attenuation coefficient k toa light at a wavelength of 193 nm ranging from 0.20 to 0.60.
 11. Amethod of forming an anti-reflective coating for use in a manufacture ofa semiconductor device, comprising the steps of: coating the compositionfor forming anti-reflective coating according to claim 1 on a substrate,and baking it.
 12. A method of forming an anti-reflective coating foruse in a manufacture of a semiconductor device by use of a light ofwavelength 248 nm, 193 nm or 157 nm, comprising the steps of: coatingthe composition for forming anti-reflective coating according to claim 1on a substrate, and baking it.
 13. A method of forming a photoresistpattern for use in a manufacture of a semiconductor device comprisingthe steps of: coating the composition for forming anti-reflectivecoating according to claim 1 on a semiconductor substrate and baking itto form an anti-reflective coating, forming a photoresist layer on theanti-reflective coating, exposing the semiconductor substrate coveredwith the anti-reflective coating and the photoresist layer with a light,and developing the exposed photoresist layer.
 14. The method of forminga photoresist pattern according to claim 13, wherein the exposure iscarried out with a light of wavelength 248 nm, 193 nm or 157 nm.